Polymerized ionic liquid block copolymers as battery membranes

ABSTRACT

The present invention is directed to compositions useful for use in separators for use in lithium ion batteries, and membranes, separators, and devices derived therefrom.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of PCT/US13/58930, filed Sep. 10,2013, which claims the benefit of priority to U.S. Patent ApplicationSer. No. 61/699,940, filed Sep. 12, 2012, the contents of each of whichis incorporated by reference in its entirety for any and all purposes.

GOVERNMENT RIGHTS

The subject matter disclosed herein was made with government supportunder contract/grant number W911NF-07-1-0452, Ionic Liquids inElectro-Active Devices (ILEAD) MURI), awarded by the Army ResearchOffice. The Government has certain rights in the herein disclosedsubject matter.

TECHNICAL FIELD

The present invention is directed to compositions useful for use inmembranes for sustainable transport of hydroxide (e.g., in fuel cells)and separators for use in lithium ion batteries, and membranes,separators, and devices derived therefrom

BACKGROUND Summary

The present invention is directed to compositions useful for use inmembranes for sustainable transport of hydroxide (e.g., in fuel cells)and separators for use in lithium ion batteries, and membranes,separators, and devices derived therefrom.

Certain embodiments of the present invention provide compositions, eachcomposition comprising block copolymer comprising at least a first andsecond block, said second block copolymer comprising (or consistingessentially of) a polymer comprising tethered ionic liquid, said polymercomprising a tethered ionic liquid cation and an associated anion, saidsecond block being stable in the presence of aqueous hydroxide, andwherein said block copolymer composition exhibits at least one region ofnanophase separation. In certain of these embodiments, the materials arecapable of sustainably transporting hydroxide therethrough. Some ofthese compositions include polymer electrolytes comprising these blockcopolymers as an effective component. Other embodiments provide polymerelectrolyte membranes comprising a polymer electrolyte as disclosedherein. Still other embodiments provide polymer electrolyte compositemembranes each comprising a polymer electrolyte described herein and aporous substrate. Yet other embodiments provide membranes as describedherein, adapted for use as a membrane in a fuel cell, including membraneelectrode assemblies derived therefrom. Particular embodiments includethose wherein these membrane electrode assemblies further comprising anickel or silver or other non-noble metal catalyst.

Other embodiments further provide a fuel cell or other energy storagedevice comprising a membrane or membrane assembly or separatorcomprising the hydroxide stable compositions described here. Otherembodiments provide for the storage or discharge of energy using a fuelcell or other energy storage device comprising the membrane or membraneassembly or separator comprising the compositions described herein.

In separate embodiments, the invention provides block copolymers, eachcomprising a first and second block, said second block comprising (orconsisting essentially of) a polymer comprising tethered ionic liquid,said polymer comprising a tethered ionic liquid cation and a mobileanion, and further comprising a lithium ion salt of said anion, whereinsaid block copolymer exhibits at least one region of nanophaseseparation. In other embodiments, these lithium ion-containingcompositions are adapted for use as a membrane in a lithium ion battery.In further embodiments, these lithium ion membranes may be incorporatedinto membrane electrode assemblies and/or a secondary lithium ionbattery.

BRIEF DESCRIPTION OF THE DRAWINGS

The present application is further understood when read in conjunctionwith the appended drawings. For the purpose of illustrating the subjectmatter, there are shown in the drawings exemplary embodiments of thesubject matter; however, the presently disclosed subject matter is notlimited to the specific methods, devices, and systems disclosed. Inaddition, the drawings are not necessarily drawn to scale. In thedrawings:

FIG. 1 show SEC chromatograms of PMMA macro-CTA, PIL block copolymerprecursor (poly(MMA-b-MEBIm-Br-13.3)), and PIL random copolymerprecursor (poly(MMA-r-MEBIm-Br-12.7)), as described in Example 1.4.

FIG. 2A-C show ¹H NMR spectra of (FIG. 2A) PMMA macro-CTA, (FIG. 2B) PILblock copolymer precursor (poly(MMA-b-MEBIm-Br-13.3)), and (FIG. 2C) PILblock copolymer (poly(MMA-b-MEBIm-TFSI-13.4)) in DMSO-d₆. PILcompositions are calculated from relative integrations of resonances“c+d” versus resonance “a” (i.e., (c+d)/2/((c+d)/2+a/3)). See Example1.4.

FIG. 3A-B show DSC thermograms of PIL (FIG. 3A) block and (FIG. 3B)random copolymers (with TFSI counteranions) at various PIL compositionsfrom 0 to ca. 15 mol % (ca. 45 vol %, Table 1); FIG. 3C shows glasstransition temperatures as a function of PIL composition. The solid linecorresponds to the Gordon-Taylor equation and the dashed linescorrespond to the PMMA and PIL homopolymer T_(g)s; FIG. 3D-E shows TGAthermograms of PIL (FIG. 3D) block and (FIG. 3E) random copolymers as afunction of PIL composition. Numbers on graph correspond to PILcomposition (mole %), as described in Example 1.5.

FIG. 4A-B shows through-plane small angle X-ray scattering profiles ofPIL (FIG. 4A) block and (FIG. 4B) random copolymers (containing TFSIcounteranions), as described in Example 1.6. Numbers on graph correspondto PIL composition (mole %). Data in (FIG. 4A) is vertically offset forclarity.

FIG. 5A shows in-plane SAXS profiles of PIL block copolymers (containingTFSI counter anions), as described in Example 1.6. Numbers on graphcorrespond to PIL composition (mole %). Data is vertically offset forclarity. FIG. 5B shows SAXS for a PIL block copolymer (PIL=15.7 mole %;TFSI counter anions) as a function of temperature. Data is verticallyoffset for clarity.

FIG. 6 is a TEM image of a PIL block copolymer,poly(MMA-b-MEBIm-TFSI-13.4), as described in Example 1.6. FFTs of imagesfind characteristic lengths of 12 to 15 nm.

FIG. 7 shows data for the temperature-dependent ionic conductivity for(a) PIL block copolymers (circles) and (b) PIL random copolymers(squares) copolymers with TFSI counteranions with comparable PILcomposition, as described in Example 1.7.

FIG. 8 shows data for the temperature-dependent ionic conductivity ofPIL block (circles) and random (squares) copolymers as a function of PILcomposition. Numbers on graph correspond to PIL composition (mole %), asdescribed in Example 1.7.

FIG. 9 shows data for the ionic conductivities at 150° C. of PIL blockcopolymers (circles) and PIL random copolymers (squares) with TFSIcounteranions as a function of PIL composition (vol %). The PILhomopolymer conductivity is shown for reference, as described in Example1.7.

FIG. 10A-D shows ¹H nmr spectra for the of poly(S-b-AEBIm-TFSI) blockcopolymers and intermediates, as described in Example 2.4.

FIG. 11A-C provides the (FIG. 11A) chemical structures of PIL blockcopolymers: BCP 1, poly(S-b-AEBIm-TFSI); BCP 2, poly(MMA-b-MEBIm-TFSI);and BCP 3, poly(S-b-VBHIm-TFSI), (FIG. 11B) ionic conductivity and (FIG.11C) morphology factors of PIL block copolymers(poly(S-b-AEBIm-TFSI-17.0), circle; poly(S-b-VBHIm-TFSI-17.0), diamond);poly(MMA-b-MEBIm-TFSI-15.7), triangle.

FIG. 12 show SEC chromatograms of PS macro-CTA and poly(S-b-BrEA-12.2),as described in Example 2.4.

FIG. 13 shows DSC thermograms of poly(S-b-AEBIm-TFSI) at various PILcompositions, as described in Example 2.4. Dashed lines correspond tothe T_(g)s of homopolymers.

FIG. 14 shows through-plane small-angle X-ray scattering profiles ofpoly(S-b-AEBIm-TFSI) as a function of PIL composition (all cast fromTHF, and solvent evaporation for ˜12 h), as described in Example 2.4.Data are offset vertically for clarity. The inverted filled triangles(▾) of 6.6 mol % and 12.2 mol % indicate expected peak positions at q*,√3q*, 2q*, √7q* for hexagonally packed cylindrical morphology. Theinverted open triangles (∇) of 17.0 mol % and 23.6 mole % indicateexpected peak positions at q*, 2q*, 3q*, and 4q* for lamellarmorphology. The arrows (↓) of 23.6 mol % indicate observed peakpositions for network (reminiscent of gyroid) morphology.

FIG. 15 shows small-angle X-ray scattering profiles ofpoly(S-b-AEBIm-TFSI-23.6) cast at different conditions (SE=solventevaporation), as described in Example 2.4. Data are offset verticallyfor clarity. The inverted open triangles (∇) of 23.6 mole % indicateexpected peak positions at q*, 2q*, 3q*, and 4q* for lamellarmorphology. The arrows (↓) of 23.6 mol % indicate observed peakpositions for network (reminiscent of gyroid) morphology.

FIG. 16A shows TEM images of poly(S-b-AEBIm-TFSI) at various PILcompositions (all cast from THF, and solvent evaporation for ˜12 h): (a)the lowest composition at 6.6 mol % (18.3 vol %), (b) the intermediatecomposition at 17.0 mol % (41.0 vol %), (c) and (d) the highestcomposition at 23.6 mol % (51.1 vol %). Dark microdomains correspond tothe AEBIm-TFSI phase. FIG. 16B shows TEM images ofpoly(S-b-AEBIm-TFSI-23.6) cast at different conditions: (e) cast fromacetonitrile with solvent evaporation for ˜12 h, and (f) cast from THFwith solvent evaporation for ˜120 h.

FIG. 17A-B shows the temperature-dependent (FIG. 17A) ionic conductivityand (FIG. 17B) morphology factors of poly(S-b-AEBIm-TFSI) as a functionof PIL composition (all cast from THF, and solvent evaporation for ˜12h), as described in Example 2.4.

FIG. 18A-B shows the temperature-dependent (FIG. 18A) ionicconductivities, and (FIG. 18B) morphology factors ofpoly(S-b-AEBIm-TFSI-23.6) cast from different solvents (both solventevaporation for ˜12 h), as described in Example 2.4.

FIG. 19 shows the ionic conductivity of PIL homopolymers as a functionof temperature (HP 1=poly(AEBIm-TFSI), triangle; HP 2=poly(VBHIm-TFSI),circle; HP 3=poly(MEBIm-TFSI), square), as described in Example 2.4.

FIG. 20 shows the ionic conductivity of PIL block copolymers as afunction of T-T_(g) (HP 1=poly(AEBIm-TFSI), triangle; HP2=poly(VBHIm-TFSI), circle; BCP 1=poly(S-b-AEBIm-TFSI-17.0); BCP2=poly(S-b-VBHIm-TFSI-17.0), diamond), as described in Example 2.4.

FIG. 21 shows the ionic conductivity of PIL homopolymers as a functionof T-T_(g) (HP 1=poly(AEBIm-TFSI), triangle; HP 2=poly(VBHIm-TFSI),circle; HP 3=poly(MEBIm-TFSI), square), as described in Example 2.4.

FIG. 22 shows the ionic conductivity of PIL block copolymers as afunction of T-T_(g) (BCP 1=poly(S-b-AEBIm-TFSI-17.0), circle; HP2=poly(S-b-BHIm-TFSI-17.0), diamond; HP 3=poly(MMA-b-MEBIm-TFSI-15.7),triangle, T_(g) (PIL block)=63° C.), as described in Example 2.4.

FIG. 23 shows the ionic conductivity of PIL block copolymers as afunction of T-T_(g) (BCP 1=poly(S-b-AEBIm-TFSI-17.0), circle; HP2=poly(S-b-BHIm-TFSI-17.0), diamond; HP 3=poly(MMA-b-MEBIm-TFSI-15.7),triangle, T_(g) (PIL homo)=7° C.), as described in Example 2.4.

FIG. 24A-B shows DSC thermograms of (FIG. 24A) poly(MMA-b-MEBIm-Br) and(FIG. 24B) poly(MMA-r-MEBIm-Br) at various PIL compositions with PMMA (0mole % PIL) and PIL (100 mole % PIL) homopolymers as control samples, asdescribed in Example 3.4.

FIG. 25A-B shows small angle X-ray scattering profiles of (FIG. 25 A)poly(MMA-b-MEBIm-Br) as a function of MEBIm-Br composition (datacollected under vacuum at 25° C. and 0% RH) and (FIG. 25B) the PIL blockcopolymer (poly(MMA-b-MEBIm-Br-17.3)) as a function of humidity andtemperature (data collected in an EC unit), as described in Example 3.Data is offset vertically for clarity.

FIG. 26A-B shows (FIG. 26A) Lattice parameter and (FIG. 26B) domain sizeof PIL (a_(PIL)) and PMMA (a_(PMMA)) blocks forpoly(MMA-b-MEBIm-Br-17.3) as a function of humidity at 30° C., asdescribed in Example 3. Data at 1% RH was taken at 25° C.

FIG. 27 shows TEM image of poly(MMA-b-MEBIm-Br) with MEBIm-Brcomposition of 17.3 mole %, as described in Example 3.

FIG. 28 shows small-angle X-ray scattering profiles of precursor PILrandom copolymers as function of PIL compositions at 25° C. and 0% RH,as described in Example 3.

FIG. 29A-B shows water uptake of (FIG. 29A) poly(MMA-b-MEBIm-OH-17.3)(squares), poly(MMA-r-MEBIm-OH-17.3) (diamonds) copolymers and PILhomopolymer (circles) and (FIG. 29B) their precursor PIL polymers as afunction of relative humidity at 30° C., as described in Example 3.5.

FIG. 30A-B shows water uptake of PIL block (poly(MMA-b-MEBIm-Br))(squares) and random (poly(MMA-r-MEBIm-Br)) (diamonds) copolymers andPIL homopolymer (poly(MEBIm-Br)) (circles) as a function of (FIG. 30A)humidity at 30° C. and (FIG. 30B) temperature at 90% RH, as described inExample 3.5.

FIG. 31 shows water uptake of anion exchange PIL block(poly(MMA-b-MEBIm-OH)) (squares) and random (poly(MMA-r-MEBIm-OH))(diamonds) copolymers and anion exchange PIL homopolymer(poly(MEBIm-OH)) (circles) as a function of temperature at 90% RH, asdescribed in Example 3.5.

FIG. 32A-B shows ionic conductivity of (FIG. 32A)poly(MMA-b-MEBIm-OH-17.3) (squares), poly(MMA-r-MEBIm-OH-17.3)(diamonds) copolymers and PIL homopolymer (circles) and (FIG. 32B) theirprecursor PIL polymers as a function of relative humidity at 30° C., asdescribed in Example 3.6.

FIG. 33A-B shows ionic conductivity of (FIG. 33A)poly(MMA-b-MEBIm-OH-17.3) (squares), poly(MMA-r-MEBIm-OH-17.3)(diamonds) copolymers and PIL homopolymer (circles) and (FIG. 33B) theirprecursor PIL polymers as a function of relative humidity at 30° C., asdescribed in Example 3.6.

FIG. 34A-B shows ionic conductivity of PIL block (poly(MMA-b-MEBIm-Br))(squares) and random (poly(MMA-r-MEBIm-Br)) (diamonds) copolymers as afunction of (FIG. 29A) humidity at 30° C. and (FIG. 34B) temperature at90% RH, as described in Example 3.6.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present invention may be understood more readily by reference to thefollowing description taken in connection with the accompanying Figuresand Examples, all of which form a part of this disclosure. It is to beunderstood that this invention is not limited to the specific products,methods, conditions or parameters described and/or shown herein, andthat the terminology used herein is for the purpose of describingparticular embodiments by way of example only and is not intended to belimiting of any claimed invention. Similarly, unless specificallyotherwise stated, any description as to a possible mechanism or mode ofaction or reason for improvement is meant to be illustrative only, andthe invention herein is not to be constrained by the correctness orincorrectness of any such suggested mechanism or mode of action orreason for improvement. Throughout this text, it is recognized that thedescriptions refer both to the features and methods of making and usingsuperhydrophobic coatings.

In the present disclosure the singular forms “a,” “an,” and “the”include the plural reference, and reference to a particular numericalvalue includes at least that particular value, unless the contextclearly indicates otherwise. Thus, for example, a reference to “amaterial” is a reference to at least one of such materials andequivalents thereof known to those skilled in the art, and so forth.

When a value is expressed as an approximation by use of the descriptor“about,” it will be understood that the particular value forms anotherembodiment. In general, use of the term “about” indicates approximationsthat can vary depending on the desired properties sought to be obtainedby the disclosed subject matter and is to be interpreted in the specificcontext in which it is used, based on its function. The person skilledin the art will be able to interpret this as a matter of routine. Insome cases, the number of significant figures used for a particularvalue may be one non-limiting method of determining the extent of theword “about.” In other cases, the gradations used in a series of valuesmay be used to determine the intended range available to the term“about” for each value. Where present, all ranges are inclusive andcombinable. That is, references to values stated in ranges include everyvalue within that range.

It is to be appreciated that certain features of the invention whichare, for clarity, described herein in the context of separateembodiments, may also be provided in combination in a single embodiment.That is, unless obviously incompatible or specifically excluded, eachindividual embodiment is deemed to be combinable with any otherembodiment(s) and such a combination is considered to be anotherembodiment. Conversely, various features of the invention that are, forbrevity, described in the context of a single embodiment, may also beprovided separately or in any sub-combination. It is further noted thatthe claims may be drafted to exclude any optional element. As such, thisstatement is intended to serve as antecedent basis for use of suchexclusive terminology as “solely,” “only” and the like in connectionwith the recitation of claim elements, or use of a “negative”limitation. Finally, while an embodiment may be described as part of aseries of steps or part of a more general structure, each said step mayalso be considered an independent embodiment in itself.

The transitional terms “comprising,” “consisting essentially of,” and“consisting” are intended to connote their generally in acceptedmeanings in the patent vernacular; that is, (i) “comprising,” which issynonymous with “including,” “containing,” or “characterized by,” isinclusive or open-ended and does not exclude additional, unrecitedelements or method steps; (ii) “consisting of” excludes any element,step, or ingredient not specified in the claim; and (iii) “consistingessentially of” limits the scope of a claim to the specified materialsor steps “and those that do not materially affect the basic and novelcharacteristic(s)” of the claimed invention. Embodiments described interms of the phrase “comprising” (or its equivalents), also provide, asembodiments, those which are independently described in terms of“consisting of” and “consisting essentially of.” For those embodimentsprovided in terms of “consisting essentially of,” the basic and novelcharacteristic(s) is the operability of the compositions (or the systemsusing in such compositions or methods of use derived therefrom) aseither hydroxide or lithium ion transport media.

When a list is presented, unless stated otherwise, it is to beunderstood that each individual element of that list, and everycombination of that list, is a separate embodiment. For example, a listof embodiments presented as “A, B, or C” is to be interpreted asincluding the embodiments, “A,” “B,” “C,” “A or B,” “A or C,” “B or C,”or “A, B, or C.”

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although any methods andmaterials similar or equivalent to those described herein can also beused in the practice or testing of the present invention, representativeillustrative methods and materials are described herein.

Hydroxide Stable Compositions, Including Hydroxide Conducting EnergyDevices

Certain embodiments of the present invention provide compositions, eachcomposition comprising block copolymer comprising at least a first andsecond block, said second block copolymer comprising a polymerized ionicliquid, said polymerized ionic liquid being stable in the presence ofaqueous hydroxide, and wherein said block copolymer composition exhibitsat least one region of nanophase separation. In other embodiments, thesehydroxide-stable compositions comprise a second block consistingessentially of polymerized monomers comprising at least one type ofionic liquid, wherein the basic and novel properties of the inventionare the hydroxide stability and the ability to sustainably transporthydroxide ions therethrough. In various embodiments, the first andsecond blocks are compositionally different. In other embodiments, thecomposition is a diblock copolymer.

As used throughout this specification, reference to “a block copolymercomprising at least a first and second block” should be well understoodby the skilled artisan as including those embodiments where the blockcopolymer contains additional blocks—e.g., triblocks (e.g., ABA, ABC),tetrablocks, pentablocks (e.g., ABCBA).

As used throughout this specification, the term “polymerized ionicliquid” is intended to connote a polymer or polymer segment or block,wherein a polymer backbone has at least one pendant comprising thecationic moiety of an ionic liquid attached thereto. It is notnecessarily intended to refer to a polymer derived from monomersoriginally having such pendants, though such materials are also withinthe scope of the present invention. That is, a polymerized ionic liquidmay or may not be made from the attachment of the cationic moiety of anionic liquid to a pre-prepared polymer backbone. See, e.g., the Examplesfor non-limiting exemplars of such strategies.

As used herein, the term “stable” as used in the terms “hydroxidestable” or “stable in the presence of aqueous hydroxide” refers to thechemical stability of the pendant moiety of the polymerized ionicliquid, when subjected to ambient temperatures in the presence ofaqueous hydroxides. In certain embodiments, this refers to (a) less than10% degradation of the polymerized ionic ligand when subjected to 1Maqueous KOH at 25° C. or less for 24 hours; or (b) less than 20%degradation when the polymerized ionic ligand when subjected to 1Maqueous KOH at temperatures up to 80° C. for 24 hours. Separateembodiments include those compositions which are at least as stable asreported for poly(MEBIm-OH) when tested under the descriptions describedin Ye, et al., “Relative Chemical Stability of Imidazolium-BasedAlkaline Anion Exchange Polymerized Ionic Liquids,” Macromolecules 2011,44, 8494-8503, which is incorporated by reference herein in its entiretyfor all purposes.

Also, as used throughout this specification, the term “nanophaseseparation” may also be described as “microphase separated morphology,”and is recognized by those skilled in the art of block copolymers. Suchseparations or morphologies may also be describes as a “self-assembly ofblocks which form a periodic nanostructured lamellar morphology withconnected ion-conducting domains due to the strong microphase separationof the hydrophilic and hydrophobic blocks.” In the instant descriptions,the first block comprises the hydrophobic block and the second blockcomprises the hydrophilic block.

In various embodiments, the at least one region of nanophase separationis characterized by at least one region of a periodic nanostructuredlamellar morphology with connected ion-conducting domains. Inindependent embodiments, the connected ion-conducting domains extend inat least two-, and preferably three-dimensions throughout the blockcopolymer. The periodicity of the nanostructured lamellar morphology maybe characterized by ordered domains having lattice parameter dimensionsin the range of about 5 to about 100 nm, as measured by small angleX-ray scattering. In independent embodiments, these ordered domains mayhave lattice parameter dimensions in ranges wherein the lower end of therange is about 5 nm, about 10 nm, about 15 nm, about 20 nm, about 25 nm,about 30 nm, about 40 nm, or about 50 nm, and the upper end of the rangeis independently about 100 nm, about 90 nm, about 80 nm, about 70 nm,about 60 nm, or about 50 nm. In exemplary, non-limiting embodiments, thedomains have lattice parameters in a range of about 5 nm to about 50 nm,about 5 nm to about 30 nm, or about 10 nm to about 30 nm.

As described herein, the first block may also be characterized as aplastic or a glassy block of hydrophobic polymer or copolymer. Inseparate embodiments, the first block may comprise polymers orcopolymers comprising an acrylate, methacrylate, styrene, orvinylpyridine derivative, or a combination thereof. Exemplary,non-limiting examples of this first block may include polymers orco-polymers comprising styrene or styrene derivatives such as, forexample, α-methylstyrene, methylstyrene, chlorostyrene, hydroxystyrene,and vinylbenzyl chloride. Other examples of plastic polymers includepolymers of indene, indene derivatives such as, for example,methylindene, ethylindene, and trimethylindene, vinylpyridine,vinylpyridine derivatives such as for example, vinylmethylpyridine,vinylbutylpyridine, vinylquinioline, and vinylacrydine, methylmethacrylate, methacrylate derivatives such as, for example,hydroxyethyl methacrylate or dimethylamino-ethyl methacrylate, andvinylcarbazole. The plastic block may be a copolymer such as, forexample, copolymers of styrene and styrene derivatives, copolymers ofmethyl methacrylate and methacrylate derivatives, copolymers of indeneand indene derivatives, copolymers of vinylpyridine and vinylpyridinederivatives copolymers of α-methylstyrene, methylstyrene and indene,copolymers of vinylpyridine and methyl methacrylate, and copolymers ofstyrene and vinylbenzyl chloride. Preferred independent embodimentsinclude those where the first block comprises a polymer or copolymercomprising a styrene derivative and/or where the first block comprises apolymer or copolymer comprising an acrylate or methacrylate derivative.

In other preferred embodiments, the block copolymer comprises a firstblock having a repeating unit according to:

where R¹, R², R³, and R⁴ are independently H or C₁₋₆ alkyl. Additionalindependent embodiments provide compositions wherein: (a) R¹ and R² areboth H; (b) both R³ and R⁴ are both C₁₋₃ alkyl; and/or (c) R¹ and R² areboth H and R³ and R⁴ are both methyl.

The first block of these copolymers may be characterized as having anumber average molecular weight. While not necessarily limited to anyparticular number average molecular weight, in certain separateindependent embodiments, the number average molecular weight of thefirst block is in a range bounded at the lower end by a value of about500, about 1000, about 2000, about 3000, about 5000, about 10,000, about20,000, or about 50,000 Daltons, and bounded at the upper end by a valueof about 1 million, about 500,000, about 100,000, about 80,000, about70,000, about 60,000, about 50,000, about 40,000, about 30,000, or about20,000 Daltons, as measured by size exclusion chromatography. In someexemplary, non-limiting embodiment, the number average molecular weightis in a range of from about 1000 to about 70,000 Daltons or from about5,000 to about 20,000 Daltons.

The second block of the block copolymers includes those where thependant cation of the ionic liquid comprises an optionally substitutedimidazolium, pyridinium, pyrrolidinium cation, or combination thereof.In addition to the pendant linking group, these cations may be mono-,di-, or tri-substituted, typically alkyl substituted, where each alkylindependently defined to include C₁₋₈ linear, branched, or cyclic carbonmoieties. The second block may comprise or consist essentially of thesetethered imidazolium, pyridinium, pyrrolidinium cations, or combinationthereof. That is, the second block may contain at least 40% polymerizedionic liquid content, at least 10%, at least 20%, at least 30%, at least40%, at least 50%, at least 60%, at least 70%, at least 80%, at least90%, at least 95%, at least 98%, or essentially 100% polymerized ionicliquid content (as a percentage of repeating units containing the cationrelative to the total repeating units in that block). To the extent thatthe second block contains a repeating unit which does not contain atethered ionic liquid cation, this repeating unit should behydrolytically stable and not compromise the intended ability totransport hydroxide ions.

In preferred embodiments, the pendant cation of the ionic liquidcomprises a C₃₋₆ alkyl-substituted imidazolium cation. In otherpreferred embodiments, the pendant ionic liquid comprises a carboalkoxy,carboxylato, carboxyamino, or ether linking group. The pendant itselfmay also comprise alkylene, alkenylene, or ether linkages, or acombination thereof. In still other preferred embodiments, thepolymerized ionic liquid comprises a repeating unit according to:

where R⁵, R⁶, R⁷, and R⁸ are independently H or optionally substitutedC₁₋₁₂ alkyl; and n has a value in a range from 0 to about 20, or from 0to about 10, or from 0 to about 5. Additional independent embodimentsprovide compositions wherein: (a) R⁵ and R⁶ are both H; (b) R⁷ and R⁸are both C₁₋₆ alkyl; and/or (c) R⁵ and R⁶ are both H, R⁷ is methyl, andR⁸ is n-butyl, and n is 1 or about 10.

In further embodiments of the hydroxide stable composition, the secondblock further comprises hydroxide counterions, either in the presence orabsence of water. In additional embodiments of the hydroxide stablecomposition, the counterions may additionally include aqueous oranhydrous alkyl phosphate, biscarbonate, bistriflimide ((i.e.,N(SO₂CF₃)₂ ⁻)), N(SO₂C₂F₅)₂ ⁻, N(SO₂CF₃)(SO₂C₄F₉)⁻, carbonate, chlorate,formate, glycolate, halide (including, e.g., fluoro, chloro, bromo,iodo), perchlorate, hexasubstituted phosphate (including PF₆ ⁻,PF₃(CF₃)₃ ⁻, PF₃(C₂F₅)₃ ⁻); tetra-substituted borate (including e.g.,BF₄ ⁻, B(CN)₄ ⁻, optionally fluorinated C₁₋₄ alkyl-BF₃ ⁻ (includingBF₃(CH₃)⁻, BF₃(CF₃)⁻, BF₃(C₂H₅)⁻, BF₃(C₂F₅)⁻, BF₃(C₃F₇)⁻), tosylate, ortriflate.

In various independent embodiments of the compositions described herein,the second block comprising the pendant ionic liquid ionic liquid has anumber average molecular weight in a range bounded at the lower end by avalue of about 250, about 500, about 1000, about 2500, about 5,000,about 10,000, or about 25,000 Daltons, and bounded at the upper end by avalue of about 1 million, about 500,000, about 100,000, about 80,000,about 70,000, about 60,000, about 50,000, about 40,000, about 30,000, orabout 20,000 Daltons, as measured by size exclusion chromatography.Exemplary non-limiting embodiments provide a range of from about 1000 toabout 70,000 Daltons or from about 5000 to about 20,000 Daltons.

The total number average molecular weight of the total block copolymeris not necessarily limited, except to the extent necessary provide atleast one region of nanophase separation. But certain independentembodiments, the block copolymer itself has a number weighted molecularweight in a range bounded at the lower end by a value of about 2500,about 5000, about 10,000, about 15,000, or about 20,000 Daltons andbounded at the upper end of the range by a value of about 1 million,about 500,000, about 100,000, about 80,000, about 70,000, about 60,000,about 50,000, about 40,000, about 30,000, about 25,000, or about 20,000Daltons, as measured by size exclusion chromatography. Exemplary,non-limiting, embodiments provide compositions having a number averagemolecular weight in the range of from about 5000 to about 25,000 Daltonsor in the range of from about 10,000 to about 25,000 Daltons, or in therange of about 15,000 to about 25,000 Daltons.

The block copolymers may be prepared by a controlled RAFT polymerizationtechnique, such that the relative lengths of the two blocks may becontrolled with good accuracy. The resulting copolymers may becharacterized has exhibiting a polydispersity in the range of about 1 toabout 2 or in the range of about 1 to about 1.5, as measured by sizeexclusion chromatography.

The block copolymers may also be characterized by the proportion of thesecond block (i.e., the content of the polymerized ionic liquid)relative to the first content. In independent embodiments, the secondblock comprising the polymerized ionic liquid is present in a range ofabout 5 mole % to about 95 mole %, or in a range of from about 5 mole %to about 50 mole %, of the total block copolymer. In certain of theseembodiments, the second block is present in a range of from about 5 toabout 10 mole %, from about 10 to about 20 mole %, from about 20 toabout 30 mole %, from about 30 to about 40 mole %, from about 40 toabout 50 mole %, from about 50 to about 70 mole % from about 70 to about95 mole %, or a range combining these ranges. In other specificembodiments, the second block comprises about 7%, about 12%, about 17%,and about 25% by mole relative to the total block copolymer (where mole% or mole content refers to percentage or content of repeating units inthe second block relative to the amount of repeating units in the totalpolymer).

In further embodiments of the hydroxide stable compositions, thecopolymer also comprises water, present in a range of from about 1 wt %to about 50 wt %, relative to the total combined weight of the blockcopolymer and the water. In other embodiments, the water may be presentin a range having a lower value of about 1 wt %, about 2 wt %, about 5wt %, about 10 wt % or about 20 wt % and having an upper value of about60 wt %, about 50 wt %, about 40 wt %, about 30 wt %, or about 20 wt %,with exemplary ranges of about 1 wt % to about 16 wt %, or in a range ofabout 1 wt % to about 10 wt %, relative to the combined weight of theblock copolymer and water.

In certain embodiments of the hydroxide stable block copolymers, theperiodic nanostructured lamellar morphology with connectedion-conducting domains allows for the conduction of aqueous hydroxideions through the block copolymer. In some embodiments, the conductivityof hydroxide through the block copolymer, at 30° C., is independently atleast: (a) about 1.6×10⁻⁵ S cm⁻¹ at a water content of about 4 wt %,relative to the total weight of the water and copolymer; or (b) about1.6×10⁻⁴ S cm⁻¹ at a water content of about 6 wt %, relative to thetotal weight of the water and copolymer; or (c) about 1×10⁻³ S cm⁻¹ at awater content of about 10 wt %, relative to the total weight of thewater and copolymer; or (d) about 1×10⁻² S cm⁻¹ at a water content ofabout 16 wt %, relative to the total weight of the water and copolymer.The conductivity of the hydroxide may further be characterized in thesecompositions having periodic nanostructured lamellar morphology as beingat least an order of magnitude (i.e., at least 10 times) higher than theconductivity of hydroxide through a compositionally equivalent, butrandom copolymer.

To this point, the various embodiments have been described mostly interms of the compositions themselves, but it should be appreciated thatthe present invention also contemplates membranes and devices comprisingthese compositions. That is, various embodiments of the presentinvention include a polymer electrolyte comprising any of the blockcopolymers described thus far as an effective component. Otherembodiments provide polymer electrolyte membranes comprising a polymerelectrolyte as just immediately described. These polymer electrolytesmay be incorporated into composite membranes, each further comprising aporous substrate. These membranes may also be adapted for use in a fuelcell, for example in the form of a membrane electrode assemblycomprising a membrane and at least one catalysts or catalytically activeelectrode. Such catalyst or catalytically active electrode may comprisea noble or non-noble metal catalyst, as is known for use in fuel cells,but particularly attractive embodiments include those wherein thecatalyst or catalytically active electrode comprises a non-noble metalcatalyst, for example nickel or silver. These compositions, polymerelectrolyte membranes composite membranes, and/or membrane assemblyelectrodes may be incorporated into an energy storage device, includinga fuel cell. Each of these is considered independent embodiments of thepresent invention.

Compositions Containing Lithium Ions, Including Lithium Ion Batteries

Certain embodiments of the present invention provide block polymercompositions, each block copolymer comprising a first and second block,said second block comprising (or consisting essentially of) apolymerized ionic liquid, said polymerized ionic liquid comprising atethered cation and a mobile anion, and further comprising a lithium ionsalt of said anion, wherein said block copolymer exhibits at least oneregion of nanophase separation. In other embodiments, these lithiumion-containing compositions comprise a second block consistingessentially of polymerized monomers having at least one type of tetheredionic liquid. In various embodiments, the first and second blocks arecompositionally different. In other embodiments, the composition is adiblock copolymer, a triblock copolymer, or a pentablock copolymer.

Again, for the sake of clarity, as used throughout this specification,the term “polymerized ionic liquid” is intended to connote a polymer orpolymer segment or block, wherein a polymer backbone has at least onependant comprising the cationic moiety of an ionic liquid attachedthereto. It is not necessarily intended to refer to a polymer derivedfrom monomers originally having such pendants, though such materials arealso within the scope of the present invention. That is, a polymerizedionic liquid may or may not be made from the attachment of the cationicmoiety of an ionic liquid to a pre-prepared polymer backbone.

Analogous to the descriptions provided above, in various embodiments ofthe lithium ion-containing compositions, the at least one region ofnanophase separation is characterized by at least one region of aperiodic nanostructured lamellar morphology with connectedion-conducting domains. In independent embodiments, the connectedion-conducting domains extend in two- or three-dimensions throughout theblock copolymer, allowing for the conduction of lithium ions through thestructure. The periodicity of the nanostructured lamellar morphology maybe characterized by ordered domains having lattice parameter dimensionsin the range of about 5 to about 100 nm, as measured by small angleX-ray scattering. In independent embodiments, these ordered domains mayhave lattice parameter dimensions in ranges wherein the lower end of therange is about 5 nm, about 10 nm, about 15 nm, about 20 nm, about 25 nm,about 30 nm, about 40 nm, or about 50 nm, and the upper end of the rangeis independently about 100 nm, about 90 nm, about 80 nm, about 70 nm,about 60 nm, or about 50 nm. In exemplary, non-limiting embodiments, thedomains have lattice parameters in a range of about 5 nm to about 50 nm,about 5 nm to about 30 nm, or about 10 nm to about 30 nm.

As described herein, the first block of these lithium salt-containingblock copolymers may also be characterized as a plastic or a glassyblock of hydrophobic polymer or copolymer. In separate embodiments, thefirst block may comprise polymers or copolymers comprising an acrylate,methacrylate, styrene, or vinylpyridine derivative, or a combinationthereof. Exemplary, non-limiting examples of this first block mayinclude polymers or copolymers comprising styrene or styrene derivativessuch as, for example, α-methylstyrene, methylstyrene, chlorostyrene,hydroxystyrene, and vinylbenzyl chloride. Other examples of plasticpolymers include polymers of indene, indene derivatives such as, forexample, methylindene, ethylindene, and trimethylindene, vinylpyridine,vinylpyridine derivatives such as for example, vinylmethylpyridine,vinylbutylpyridine, vinylquinioline, and vinylacrydine, methylmethacrylate, methacrylate derivatives such as, for example,hydroxyethyl methacrylate or dimethylamino-ethyl methacrylate, andvinylcarbazole. The plastic block may be a copolymer such as, forexample, copolymers of styrene and styrene derivatives, copolymers ofmethyl methacrylate and methacrylate derivatives, copolymers of indeneand indene derivatives, copolymers of vinylpyridine and vinylpyridinederivatives copolymers of α-methylstyrene, methylstyrene and indene,copolymers of vinylpyridine and methyl methacrylate, and copolymers ofstyrene and vinylbenzyl chloride. Preferred independent embodimentsinclude those where the first block comprises a polymer or copolymercomprising a styrene derivative and/or where the first block comprises apolymer or copolymer comprising an acrylate or methacrylate derivative.

In certain preferred embodiments, the block copolymer of thesecompositions comprises a first block having a repeating unit accordingto:

where R^(1A), R^(2A), R^(3A), and R^(4A) are independently H or C₁₋₆alkyl. Additional independent embodiments provide compositions wherein:(a) R^(1A) and R^(2A) are both H; (b) both R^(3A) and R^(4A) are bothC₁₋₃ alkyl; and/or (c) R^(1A) and R^(2A) are both H and R^(3A) andR^(4A) are both methyl.

Also, analogous to the descriptions above, the first block of thesecopolymers may be characterized as having a number average molecularweight. While not necessarily limited to any particular number averagemolecular weight, in certain separate independent embodiments, thenumber average molecular weight of the first block is in a range boundedat the lower end by a value of about 500, about 1000, about 2000, about3000, about 5000, about 10,000, about 20,000, or about 50,000 Daltons,and bounded at the upper end by a value of about 1 million, about500,000, about 100,000, about 80,000, about 70,000, about 60,000, about50,000, about 40,000, about 30,000, or about 20,000 Daltons, as measuredby size exclusion chromatography. In some exemplary, non-limitingembodiment, the number average molecular weight is in a range of fromabout 1000 to about 70,000 Daltons or from about 5,000 to about 20,000Daltons.

The second blocks of the block copolymers containing lithium ionsinclude those where the pendant cation of the ionic liquid comprises anoptionally alkyl-substituted imidazolium, pyridinium, pyrrolidiniumcation, or combination thereof. In addition to the pendant linkinggroup, these cations may be mono-, di-, or tri-substituted, typicallyalkyl substituted, where each alkyl independently defined to includeC₁₋₈ linear, branched, or cyclic carbon moieties. The second block maycomprise or consist essentially of these tethered imidazolium,pyridinium, pyrrolidinium cations, or combination thereof. That is, thesecond block may contain at least 40% tethered ionic liquid cationcontent, at least 10%, at least 20%, at least 30%, at least 40%, atleast 50%, at least 60%, at least 70%, at least 80%, at least 90%, atleast 95%, at least 98%, or essentially 100% polymerized ionic liquidcontent (as a percentage of repeating units containing the cationrelative to the total repeating units in that block). To the extent thatthe second block contains a repeating unit which does not contain atethered ionic liquid cation, this repeating unit should not compromisethe intended ability to transport lithium ions.

In preferred embodiments of the lithium ion-containing block copolymers,the pendant cation of the ionic liquid comprises a C₃₋₆alkyl-substituted imidazolium cation. In other preferred embodiments,the pendant ionic liquid comprises a carboalkoxy, carboxylato,carboxyamino, or ether linking group. The pendant itself may alsocomprise alkylene, alkenylene, or ether linkages, or a combinationthereof. In still other preferred embodiments, the polymerized ionicliquid comprises a repeating unit according to

where R^(5A), R^(6A), R^(7A), and R^(8A) are independently H oroptionally substituted C₁₋₁₂ alkyl; and n has a value in a range from 0to about 20, or from 0 to about 10, or from 0 to about 5. Additionalindependent embodiments provide compositions wherein: (a) R⁵ and R⁶ areboth H; (b) R⁷ and R⁸ are both C₁₋₆ alkyl; and/or (c) R⁵ and R⁶ are bothH, R⁷ is methyl, and R⁸ is n-butyl, and n is 1 or about 10.

In various independent embodiments of the lithium ion-containingcompositions, the second block comprising polymerized ionic liquid has anumber average molecular weight in a range bounded at the lower end ofabout 250, about 500, about 1000, about 2500, about 5,000, about 10,000,or about 25,000 Daltons, and bounded at the upper end of about 1million, about 500,000, about 100,000, about 80,000, about 70,000, about60,000, about 50,000, about 40,000, about 30,000, or about 20,000Daltons, as measured by size exclusion chromatography. Exemplarynon-limiting embodiments provide a range of about 1000 to about 70,000Daltons or about 5000 to about 20,000 Daltons.

The total number average molecular weight of the total lithiumion-containing block copolymer is not necessarily limited, except to theextent necessary provide at least one region of nanophase separation.But certain independent embodiments, the block copolymer itself has anumber weighted molecular weight in a range bounded at the lower end ofabout 2500, about 5000, about 10,000, about 15,000, or about 20,000Daltons and bounded at the upper end of the range of about 1 million,about 500,000, about 100,000, about 80,000, about 70,000, about 60,000,about 50,000, about 40,000, about 30,000, about 25,000, or about 20,000Daltons, as measured by size exclusion chromatography. Exemplary,non-limiting, embodiments provide compositions having a number averagemolecular weight in the range of from about 5000 to about 25,000 Daltonsor in the range of from about 10,000 to about 25,000 Daltons, or in therange of from about 15,000 to about 25,000 Daltons.

As with the hydroxide stable compositions, the lithium ion-containingblock copolymers may be prepared by a controlled RAFT polymerizationtechnique, such that the relative lengths of the two blocks may becontrolled with good accuracy. The resulting copolymers may becharacterized has exhibiting a polydispersity in the range of about 1 toabout 2 or in the range of about 1 to about 1.5, as measured by sizeexclusion chromatography.

As with the hydroxide stable compositions, the lithium ion-containingblock copolymers may also be characterized by the proportion of thesecond block (i.e., the content of the polymerized ionic liquid)relative to the first content. In independent embodiments, the secondblock comprising the polymerized ionic liquid is present in a range ofabout 5 mole % to about 95 mole %, or in a range of about 5 mole % toabout 50 mole %, of the total block copolymer. In certain of theseembodiments, the second block is present in a range of from about 5 toabout 10 mole %, from about 10 to about 20 mole %, from about 20 toabout 30 mole %, from about 30 to about 40 mole %, from about 40 toabout 50 mole %, from about 50 to about 70 mole % from about 70 to about95 mole %, or a range combining these ranges. In specific embodiments,the second block comprises about 7%, about 12%, about 17%, and about 25%by mole relative to the total block copolymer (where mole % or molecontent refers to percentage or content of repeating units in the secondblock relative to the amount of repeating units in the total polymer).

In various embodiments of the lithium ion-containing block copolymers,the second block of the block copolymer is substantially anhydrous(i.e., does not contain deliberately added water or any water addedduring processing or preparation of the composition is removed as muchas practicable). In other embodiments, the second block may compriseanhydrous solvents, for example comprising ethylene carbonate, ethyleneglycol, polyethylene glycol, propylene glycol, propylene carbonate,butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethylcarbonate, dipropyl carbonate, γ-butyrolactone, dimethoxyethane,diethoxyethane, or a mixture thereof.

In certain embodiments, these lithium ion-containing block copolymercompositions comprise lithium ions wherein the counterions may includealkyl phosphate, biscarbonate, bistriflimide ((i.e., N(SO₂CF₃)₂ ⁻)),N(SO₂C₂F₅)₂ ⁻, N(SO₂CF₃)(SO₂C₄F₉)⁻, carbonate, chlorate, formate,glycolate, perchlorate, hexasubstituted phosphate (including PF₆ ⁻⁻,PF₃(CF₃)₃ ⁻⁻, PF₃(C₂F₅)₃ ⁻⁻); tetra-substituted borate (including e.g.,BF₄ ⁻, B(CN)₄ ⁻, optionally fluorinated C₁₋₄ alkyl-BF₃ ⁻, includingBF₃(CH₃)⁻, BF₃(CF₃)⁻, BF₃(C₂H₅)⁻, BF₃(C₂F₅)⁻, BF₃(C₃F₇)⁻), tosylate, ortriflate. In other embodiments, these lithium ion-containing blockcopolymers additionally or alternatively comprise mobile (untethered)ionic liquids, said mobile ionic liquids comprising at least oneoptionally substituted imidazolium, pyridinium, pyrrolidinum cation andat least one alkyl phosphate, biscarbonate, bistriflimide ((i.e.,N(SO₂CF₃)₂ ⁻)), N(SO₂C₂F₅)₂ ⁻, N(SO₂CF₃)(SO₂C₄F₉)⁻, carbonate, chlorate,formate, glycolate, perchlorate, hexasubstituted phosphate (includingPF₆ ⁻, PF₃(CF₃)₃ ⁻, PF₃(C₂F₅)₃ ⁻); tetra-substituted borate (includinge.g., BF₄ ⁻, B(CN)₄ ⁻, optionally fluorinated C₁₋₄ alkyl-BF₃ ⁻,including BF₃(CH₃)⁻, BF₃(CF₃)⁻, BF₃(C₂H₅)⁻, BF₃(C₂F₅)⁻, BF₃(C₃F₇)⁻),tosylate, or triflate anion.

In certain embodiments, the lithium salt concentration and the mobileionic liquid concentration may independently vary such that the total isin a range of about 1% to about 50% by weight, relative to the totalweight of the block copolymer including the lithium salt and mobileionic liquid. In other independent embodiments, the lithium saltconcentration and the mobile ionic liquid concentration mayindependently vary such that the total is defined by a range having alower end of about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% by weight,and having an upper end of about 50%, about 45%, about 40%, about 35%,about 30%, about 25%, about 20% about 15%, or about 10% by weight,relative to the total weight of the block copolymer including thelithium salt or mobile ionic liquid or both. In other embodiments, theblock copolymers may be contained as additives within liquids comprisingat least one lithium salt or mobile ionic liquid or both, wherein thepolymer is present in the liquid at a concentration in a range of fromabout 1 to about 50% by weight, relative to the weight of the liquidincluding the polymer.

As used here, the term “nanophase separation” carries the same meaningas described about—i.e., it may also be described as “microphaseseparated morphology,” and is recognized by those skilled in the art ofblock copolymers. Such separations or morphologies may also be describesas a “self-assembly of blocks which form a periodic nanostructuredlamellar morphology with connected ion-conducting domains due to thestrong microphase separation of the hydrophilic and hydrophobic blocks.”In the instant descriptions, the first block comprises the hydrophobicblock and the second block comprises the hydrophilic block.

To this point, the embodiments related to the lithium ion-containingcompositions have been described mainly in terms of block copolymercompositions, but other embodiments of this invention also include thosewherein these compositions are adapted for use, and/or actually compriseor are incorporated within a lithium ion battery membrane, or a membraneelectrode assembly. Still other embodiments include those lithium ionbatteries (or reversible or irreversible energy storage and/or deliverysystems) which comprise a composition or a membrane or membraneelectrode assembly comprising a composition described herein.

The following Embodiments are meant to complement and not supersedeprevious descriptions. Among the many embodiments considered within thescope of the present invention are these:

Embodiment 1

A block copolymer comprising at least a first and second block, saidsecond block copolymer comprising a polymerized ionic liquid, saidpolymerized ionic liquid being stable in the presence of aqueoushydroxide, and wherein said block copolymer composition exhibits atleast one region of nanophase separation.

Embodiment 2

The block copolymer of Embodiment 1, wherein at least one region ofnanophase separation is characterized by at least one region of aperiodic nanostructured lamellar morphology with connectedion-conducting domains.

Embodiment 3

The block copolymer of Embodiment 2, wherein the connectedion-conducting domains extend in three-dimensions throughout the blockcopolymer.

Embodiment 4

The block copolymer of Embodiment 2 or 3, wherein the periodicity of thenanostructured lamellar morphology is characterized by ordered domainshaving lattice parameter dimensions in the range of about 5 to about 50nm, as measured by small angle X-ray scattering.

Embodiment 5

The block copolymer of any one of Embodiments 1 to 4, wherein the blockcopolymer is a diblock copolymer.

Embodiment 6

The block copolymer of any one of Embodiments 1 to 5, wherein the firstblock comprises polymers or copolymers comprising an acrylate,methacrylate, styrene, or vinylpyridine derivative, or a combinationthereof.

Embodiment 7

The block copolymer of any of one of Embodiments 1 to 6, wherein thefirst block comprises a polymer or copolymer comprising a styrenederivative.

Embodiment 8

The block copolymer of any of Embodiments 1 to 7, wherein the firstblock comprises a polymer or copolymer comprising an acrylate ormethacrylate derivative.

Embodiment 9

The block copolymer of any one of Embodiments 1 to 8, wherein the firstblock comprises a repeating unit:

where R¹, R², R³, and R⁴ are independently H or C₁₋₆ alkyl.

Embodiment 10

The block copolymer of Embodiment 9, wherein R¹ and R² are both H.

Embodiment 11

The block copolymer of Embodiment 9, wherein both R³ and R⁴ are bothC₁₋₃ alkyl.

Embodiment 12

The block copolymer of Embodiment 9, wherein R¹ and R² are both H and R³and R⁴ are both methyl.

Embodiment 13

The block copolymer of any one of Embodiments 1 to 12, wherein the firstblock has an average molecular weight in the range of about 1000 toabout 1,000,000 Daltons.

Embodiment 14

The block copolymer of any one of Embodiments 1 to 13, wherein thepolymerized ionic liquid comprises an optionally alkyl-substitutedimidazolium, pyridinium, pyrrolidinium, cation, or combination thereof.

Embodiment 15

The block copolymer of any one of Embodiments 1 to 14, wherein thepolymerized ionic liquid comprises a C₃₋₆ alkyl-substituted imidazoliumcation.

Embodiment 16

The block copolymer of any one of Embodiments 1 to 15, wherein thepolymerized ionic liquid comprises a carboalkoxy linking group.

Embodiment 17

The block copolymer of any one of Embodiments 1 to 16, wherein thepolymerized ionic liquid comprises a repeating unit:

where R⁵, R⁶, R⁷, and R⁸ are independently H or optionally substitutedC₁₋₁₂ alkyl; and n is 0 to about 20.

Embodiment 18

The block copolymer of Embodiment 17, wherein R⁵ and R⁶ are both H.

Embodiment 19

The block copolymer of Embodiment 17, wherein R⁷ and R⁸ are both C₁₋₆alkyl.

Embodiment 20

The block copolymer of Embodiment 17, wherein R⁵ and R⁶ are both H, R⁷is methyl, and R⁸ is n-butyl, and n=1.

Embodiment 21

The block copolymer of any one of Embodiments 1 to 20, wherein thesecond block comprising polymerized ionic liquid further comprisesaqueous hydroxide counterions.

Embodiment 22

The block copolymer of any one of Embodiments 1 to 21, wherein thesecond block comprising polymerized ionic liquid has an averagemolecular weight in the range of about 250 to about 1,000,000 Daltons.

Embodiment 23

The block copolymer of any one of Embodiments 1 to 22, wherein the blockcopolymer has a number weighted molecular weight in a range of about5000 to about 25,000 Daltons, as measured by size exclusionchromatography.

Embodiment 24

The block copolymer of any one of Embodiments 1 to 23, wherein the blockcopolymer has a number weighted molecular weight characterized asexhibiting a polydispersity in the range of about 1 to about 1.5, asmeasured by size exclusion chromatography.

Embodiment 25

The block copolymer of any one of Embodiments 1 to 24, wherein thesecond block comprising the polymerized ionic liquid is present in arange of about 5 mole % to about 95 mole % of the total block copolymer.

Embodiment 26

The block copolymer of any one of Embodiments 1 to 25, furthercomprising water, present in a range of about 1 wt % to about 50 wt %,relative to the total combined weight of the block copolymer and thewater.

Embodiment 27

The block copolymer of any one of Embodiments 2 to 26, wherein theperiodic nanostructured lamellar morphology with connectedion-conducting domains allows for the conduction of aqueous hydroxideions through the block copolymer.

Embodiment 28

The block copolymer of Embodiment 27, wherein the conductivity ofhydroxide through the block copolymer, at 30° C., is at least: (a) about1.6×10⁻⁵ S cm⁻¹ at a water content of about 4 wt %, relative to thetotal weight of the water and copolymer; or (b) about 1.6×10⁻⁴ S cm⁻¹ ata water content of about 6 wt %, relative to the total weight of thewater and copolymer; or (c) about 1×10⁻³ S cm⁻¹ at a water content ofabout 10 wt %, relative to the total weight of the water and copolymer;or (d) about 1×10⁻² S cm⁻¹ at a water content of about 16 wt %, relativeto the total weight of the water and copolymer.

Embodiment 29

The block copolymer of any of Embodiments 1 to 28, wherein theconductivity of hydroxide through the block copolymer is at least 10times higher than the conductivity of hydroxide through acompositionally equivalent, but random copolymer.

Embodiment 30

A polymer electrolyte comprising the block copolymer of any ofEmbodiments 1 to 29 as an effective component.

Embodiment 31

A polymer electrolyte membrane comprising the polymer electrolyte ofEmbodiment 30.

Embodiment 32

A polymer electrolyte composite membrane comprising the polymerelectrolyte of Embodiment 30, and a porous substrate.

Embodiment 33

A membrane for use in a fuel cell, comprising a block copolymer of anyone of Embodiments 1-29, adapted for use as a membrane in a fuel cell.

Embodiment 34

A membrane electrode assembly comprising a membrane of any one ofEmbodiments 31 to 33.

Embodiment 35

The membrane electrode assembly of Embodiment 34, further comprising anickel or silver catalyst.

Embodiment 36

A fuel cell comprising a membrane of any one of Embodiments 31 to 33 ora membrane electrode assembly of Embodiment 34 or 35.

Embodiment 37

An energy storage device comprising a membrane of any one of Embodiments31 to 33.

Embodiment 38

An energy storage device comprising a membrane assembly of Embodiment 34or 35.

Embodiment 39

A block copolymer comprising a first and second block, said second blockcomprising a polymerized ionic liquid, said polymerized ionic liquidcomprising a tethered ionic liquid cation and a mobile anion, andfurther comprising a lithium ion salt of said anion, wherein said blockcopolymer exhibits at least one region of nanophase separation.

Embodiment 40

The block copolymer of Embodiment 39, wherein at least one region ofnanophase separation is characterized by at least one region of aperiodic nanostructured lamellar morphology with connectedion-conducting domains.

Embodiment 41

The block copolymer of Embodiment 40, wherein the connectedion-conducting domains extend in three-dimensions throughout the blockcopolymer.

Embodiment 42

The block copolymer of Embodiment 40 or 41, wherein the periodicity ofthe nanostructured lamellar morphology is characterized by ordereddomains having lattice parameter dimensions in the range of about 5 toabout 50 nm, as measured by small angle X-ray scattering.

Embodiment 43

The block copolymer of any one of Embodiments 40 to 42, wherein theperiodic nanostructured lamellar morphology with connectedion-conducting domains allows for the conduction of lithium ions throughthe block copolymer.

Embodiment 44

The block copolymer of any one of Embodiments 39 to 43, wherein thefirst block comprises polymers or copolymers comprising an acrylate,methacrylate, styrene, or vinylpyridine derivative, or a mixturethereof.

Embodiment 45

The block copolymer of any of Embodiments 39 to 44, wherein the firstblock comprises a polymer or copolymer comprising a styrene derivative.

Embodiment 46

The block copolymer of any one of Embodiments 39 to 44, wherein thefirst block comprises polymers or copolymers comprising an acrylate ormethacrylate derivative.

Embodiment 47

The block copolymer of any one of Embodiments 39 to 44, wherein thefirst block comprises a repeating unit:

where R^(1A), R^(2A), R^(3A), and R^(4A) are independently H or C₁₋₁₂alkyl.

Embodiment 48

The block copolymer of Embodiment 47, wherein R^(1A) and R^(2A) are bothH.

Embodiment 49

The block copolymer of Embodiment 47, wherein both R^(3A) and R^(4A) areboth C₁₋₆ alkyl.

Embodiment 50

The block copolymer of Embodiment 47, wherein R^(1A) and R^(2A) are bothH and R^(3A) and R^(4A) are both methyl.

Embodiment 51

The block copolymer of any one of Embodiments 39 to 49, wherein thefirst block has an average molecular weight in the range of about 1000to about 50000 Daltons.

Embodiment 52

The block copolymer of any one of Embodiments 39 to 51, wherein thetethered ionic liquid cation comprises an optionally alkyl-substitutedimidazolium, pyridinium, pyrrolidinum cation, or combination thereof.

Embodiment 53

The block copolymer of any one of Embodiments 39 to 52, wherein thepolymerized ionic liquid comprises a C₃₋₆ alkyl-substituted imidazoliumcation.

Embodiment 54

The block copolymer of any one of Embodiments 39 to 53, wherein thecation of the polymerized is tethered by a carboalkoxy linking group.

Embodiment 55

The block copolymer of any one of Embodiments 39 to 54, wherein thesecond block comprising a polymerized ionic liquid comprises a repeatingunit:

where R^(5A), R^(6A), R^(7A), and R^(8A) are independently H or C₁₋₆alkyl; and n is in a range of 0 to 20.

Embodiment 56

The block copolymer of Embodiment 55, wherein R^(5A) and R^(6A) are bothH.

Embodiment 57

The block copolymer of Embodiment 55, wherein R^(7A) and R^(8A) are bothC₁₋₄ alkyl.

Embodiment 58

The block copolymer of Embodiment 55, wherein R^(5A) and R^(6A) are bothH, R^(7A) is methyl, and R^(8A) is n-butyl, and n=1.

Embodiment 59

The block copolymer of any one of Embodiments 39 to 58, wherein theblock copolymer is substantially anhydrous.

Embodiment 60

The block copolymer of any one of Embodiments 39 to 59, wherein thesecond block further comprises a solvent comprising ethylene carbonate,ethylene glycol, polyethylene glycol, propylene glycol, propylenecarbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate,methylethyl carbonate, dipropyl carbonate, γ-butyrolactone,dimethoxyethane, diethoxyethane, or a mixture thereof.

Embodiment 61

The block copolymer of any one of Embodiments 39 to 60, furthercomprising a lithium salt of an alkyl phosphate, biscarbonate,bistriflimide, N(SO₂C₂F₅)₂ ⁻, N(SO₂CF₃)(SO₂C₄F₉)⁻, carbonate, chlorate,formate, glycolate, perchlorate, hexasubstituted phosphate;tetra-substituted borate), tosylate, or triflate or combination thereof.

Embodiment 62

The block copolymer of any one of Embodiments 39 to 61, furthercomprising a mobile ionic liquid.

Embodiment 63

The block copolymer of Embodiment 62, wherein said mobile ionic liquidcomprising at least one optionally substituted imidazolium, pyridinium,pyrrolidinum cation and at least one alkyl phosphate, biscarbonate,bistriflimide, N(SO₂C₂F₅)₂ ⁻, N(SO₂CF₃)(SO₂C₄F₉)⁻, carbonate, chlorate,formate, glycolate, perchlorate, hexasubstituted phosphate;tetra-substituted borate), tosylate, or triflate anion.

Embodiment 64

The block copolymer of any one of Embodiments 39 to 63, wherein thepolymerized ionic liquid block has an average molecular weight in therange of about 1000 to about 50000 Daltons.

Embodiment 65

The block copolymer of any one of Embodiments 39 to 64, wherein theblock copolymer has a number weighted molecular weight in a range ofabout 5000 to about 25,000 Daltons, as measured by size exclusionchromatography.

Embodiment 66

The block copolymer of any one of Embodiments 39 to 65, wherein theblock copolymer has a number weighted molecular weight which ischaracterized as exhibiting a polydispersity in the range of about 1 toabout 1.5, as measured by size exclusion chromatography.

Embodiment 67

The block copolymer of any one of Embodiments 39 to 66, wherein thepolymerized ionic liquid block is present in a range of about 5 mole %to about 95 mole % of the total block copolymer.

Embodiment 68

A membrane for use in a lithium ion battery, comprising a blockcopolymer of any one of Embodiments 39 to 67, adapted for use as amembrane in the lithium ion battery.

Embodiment 69

A membrane electrode assembly comprising a membrane of Embodiment 68.

Embodiment 70

A lithium ion battery comprising a membrane of Embodiment 68 or amembrane electrode assembly of Embodiment 69.

EXAMPLES

The following Examples are provided to illustrate some of the conceptsdescribed within this disclosure. While each Example is considered toprovide specific individual embodiments of composition, methods ofpreparation and use, none of the Examples should be considered to limitthe more general embodiments described herein.

In the following examples, efforts have been made to ensure accuracywith respect to numbers used (e.g. amounts, temperature, etc.) but someexperimental error and deviation should be accounted for. Unlessindicated otherwise, temperature is in degrees C., pressure is at ornear atmospheric.

Example 1 Polymerized Ionic Liquid Block and Random Copolymers: Effectof Weak Microphase Separation on Ion Transport

In this study, a series of PIL diblock copolymers were synthesized from1-[(2-methacryloyloxy)ethyl]-3-butylimidazoliumbis(trifluoromethanesulfonyl)imide (MEBIm-TFSI) IL monomer and methylmethacrylate (MMA) non-ionic monomer at various PIL compositions usingthe reversible addition-fragmentation chain transfer (RAFT)polymerization technique. An analogous series of PIL random copolymersat similar PIL compositions were synthesized using conventional freeradical polymerization. The comparison of PIL block and randomcopolymers at similar PIL compositions allows for a clear understandingof the impact of morphology on ion transport in PILs. A significantincrease (2 orders of magnitude) in ionic conductivity from the randomcopolymers to the block copolymers was observed at similar PILcompositions and is attributed to the weak microphase separation in theblock copolymer morphology. These results suggest that the localconfinement of conducting ions in nanoscale ionic domains can accelerateion transport, where strong microphase separation is not required forsignificant enhancements in ion transport.

Example 1.1 Materials

4-cyano-4-(phenylcarbonothioylthio)pentanoic acid (chain transfer agent(CTA), >97%, HPLC), tetrahydrofuran (THF, ≧99.9%), N,N-dimethylformamide(DMF, 99.9%, HPLC), methanol (99.9%, HPLC), diethyl ether (≧98%),acetonitrile (anhydrous, 99.8%), calcium hydride (CaH₂, 95%), lithiumbis(trifluoromethanesulfonyl)imide (LiTFSI, 97%), lithium bromide (LiBr,≧99%) and dimethyl sulfoxide-d₆ (DMSO-d₆, 99.9 atom % D, contains 0.03%v/v TMS) were used as received from Sigma-Aldrich.Azobisisobutyronitrile (AIBN, 98%, Sigma-Aldrich) was purified byrecrystallization twice from methanol. Methyl methacrylate (MMA, 99%,Sigma-Aldrich) was purified by distillation over CaH₂ at a reducedpressure. Ionic liquid monomer,1-[(2-methacryloyloxy)ethyl]-3-butylimidazolium bromide (MEBIm-Br), wasprepared similarly according to the literature. The quaternizationreaction was carried out at room temperature for 30 hrs without using aninhibitor. Dialysis tubing (Spectra/Por biotech membrane, molecularweight cutoff (MWCO)=500) was purchased from Fisher Scientific.Ultrapure deionized (DI) water with resistivity ca. 16 MΩ cm was used asappropriate. Ionic liquid monomer, 11-Bromoundecyl methacrylate (BrUMA)was similarly prepared at room temperature for 18 hrs.

Example 1.2 PIL Block and Random Copolymer Synthesis

A series of polymerized ionic liquid (PIL) block(poly(MMA-b-MEBIm-TFSI)) and random (poly(MMA-r-MEBIm-TFSI)) copolymerswere synthesized at various MEBIm-TFSI or PIL compositions. PIL blockand random copolymer precursors bearing bromide (Br) counterions werefirst synthesized via living/controlled polymerization (reversibleaddition-fragmentation chain transfer (RAFT) polymerization) (Scheme 1a)and conventional free radical polymerization (Scheme 1b), respectively.The precursors were then subsequently converted into TFSI counterionform via salt metathesis (anion exchange) (Scheme 1).

Example 1.2.1 Synthesis of PMMA Macro-CTA

The preparation of PMMA macro-chain transfer agent (macro-CTA) is shownin Scheme 1a. 25.168 g of MMA (251.378 mmol), 141.5 mg of CTA (0.506mmol), 20.8 mg of AIBN (0.127 mmol) were mixed with 9 mL THF in a 250 mLsingle-neck Schlenk flask. The flask was subjected to 4 freeze-pump-thawdegassing cycles followed by sealing the reactor and carrying out thereaction under static vacuum at 70° C. for 5 h. The resulting polymerwas twice precipitated in methanol and dried under vacuum in an oven atroom temperature for 24 h. Yield: 9.62 g of solid particles (38.2%). ¹HNMR (500 MHz, DMSO-d₆, 23° C.) δ (ppm): 7.87-7.50 (m, C₆H₅), 3.57 (s,3H, O—CH₃), 1.84-1.76 (d, 2H, CH₂—C(CH₃)), 0.94-0.74 (d, 3H,CH₂—C(CH₃)); M_(n)=13.1 kg mol⁻¹ (NMR). SEC (DMF, 40° C.): M_(n)=12.53kg mol⁻¹, M_(w)/M_(n)=1.19 (against PEG/PEO standards).

Example 1.2.2 Synthesis of Diblock Copolymer Poly(MMA-b-MEBIm-Br)

The synthesis of the PIL block copolymer precursor(poly(MMA-b-MEBIm-Br-13.3)) is shown in Scheme 1a(2a). A typical exampleis given as follows. 3.006 g of IL monomer (MEBIm-Br) in DMF(MEBIm-Br/DMF=1/1 w/w, MEBIm-Br=4.738 mmol), 3.653 g of PMMA macro-CTAin DMF (PMMA/DMF=1/2 w/w, PMMA=0.097 mmol), 1.6 mg of AIBN (0.010 mmol)were mixed with 5 mL DMF solvent in a 50 mL Schlenk flask and subjectedto 4 freeze-pump-thaw degassing cycles. After degassing, the reactor wassealed and the reaction was then carried out under static vacuum at 70°C. for 5 h. The resulting polymer was twice precipitated in DI water andsubsequently washed extensively with DI water. The block copolymer wasfiltered and then dried under vacuum in an oven at 40° C. for 24 h.Yield: 1.365 g of solid particles (50.2%). ¹H NMR (500 MHz, DMSO-d₆, 23°C.) δ (ppm): 9.82 (s, 1H, N—CH═N), 8.02 (d, 2H, N—CH═CH—N), 4.64-4.29(d, 6H, N—CH₂—CH₂—O, N—CH₂—CH₂—CH₂), 3.57 (s, 3H, OCH₃), 1.88 (s, 4H,CH₂—C(CH₃), N—CH₂—CH₂—CH₂—CH₃), 1.32 (s, 5H, N—CH₂—CH₂—CH₂—CH₃,CH₂—C(CH₃)), 0.93 (s, 6H, N—CH₂—CH₂—CH₂—CH₃, CH₂—C(CH₃)), 0.77 (s, 3H,CH₂—C(CH₃)). SEC (DMF, 40° C.): M_(n)=22.93 kg mol⁻¹, M_(w)/M_(n)=1.31(against PEG/PEO standards).

Example 1.2.3 Synthesis of Diblock Copolymer Poly(MMA-b-MEBIm-TFSI)

The anion exchange from Br to TFSI neutralized form is shown in Scheme1a. Poly(MMA-b-MEBIm-Br-13.3) (0.317 g, 0.014 mmol) and LiTFSI (0.653 g,2.275 mmol) were mixed with DMF (5 mL) and then stirred at 50° C. for 24h. The reaction mixture was twice precipitated into methanol/water (1/1v/v) and washed extensively with DI water. The resulting polymer wasfiltered and dried under vacuum in an oven at 40° C. for 24 h. Yield:0.277 g of solid particles (72.5%). ¹H NMR (500 MHz, DMSO-d₆, 23° C.) δ(ppm): 9.24 (s, 1H, N—CH═N), 7.83-7.75 (d, 2H, N—CH═CH—N), 4.48-4.20 (d,6H, N—CH₂—CH₂—O, N—CH₂—CH₂—CH₂), 3.56 (s, 3H, OCH₃), 1.81 (s, 4H,CH₂—C(CH₃), N—CH₂—CH₂—CH₂—CH₃), 1.32 (s, 5H, N—CH₂—CH₂—CH₂—CH₃,CH₂—C(CH₃)), 0.94 (s, 6H, N—CH₂—CH₂—CH₂—CH₃, CH₂—C(CH₃)), 0.74 (s, 3H,CH₂—C(CH₃)). Elemental Anal. Calcd: C, 48.78; H, 6.30; N, 3.61; F, 9.79;S, 5.51; Br, 0.00. Found: C, 47.09; H, 5.96; N, 4.01; F, 10.66; S, 5.97;Br, <0.25.

Example 1.2.4 Synthesis of Random Copolymer Poly(MMA-r-MEBIm-Br)

The synthesis of the PIL random copolymer precursor(poly(MMA-r-MEBIm-Br-12.7)) is shown in Scheme 1b. A typical example isgiven as follows. 3.297 g of IL monomer (MEBIm-Br) in DMF(MEBIm-Br/DMF=1/1 wt/wt, MEBIm-Br=5.197 mmol), 2.351 g (23.482 mmol) ofMMA, were added to 12 mL DMF and mixed in a flask and purged with N₂ for30 min. 23.6 mg (0.144 mmol) of AIBN initiator was then added to themixture and further purged with N₂ for 10 min. The reaction was carriedout at 70° C. for 5 h. The resulting polymer was precipitated in diethylether followed by stirring in an extensive amount of DI water for 24 h.The final polymer product was dried under vacuum at 40° C. for 24 h.Yield: 1.913 g of solid particles (47.8%). ¹H NMR (500 MHz, DMSO-d₆, 23°C.) δ (ppm): 9.35 (s, 1H, N—CH═N), 7.91 (d, 2H, N—CH═CH—N), 4.52-4.24(d, 6H, N—CH₂—CH₂—O, N—CH₂—CH₂—CH₂), 3.55 (s, 3H, OCH₃), 1.84-1.75 (d,4H, CH₂—C(CH₃), N—CH₂—CH₂—CH₂—CH₃), 1.32 (s, 5H, N—CH₂—CH₂—CH₂—CH₃,CH₂—C(CH₃)), 0.94 (s, 6H, N—CH₂—CH₂—CH₂—CH₃, CH₂—C(CH₃)), 0.73-0.55 (d,3H, CH₂—C(CH₃)). SEC (DMF, 40° C.): M_(n)=29.83 kg mol⁻¹,M_(w)/M_(n)=2.28 (against PEG/PEO standards).

Example 1.2.5 Synthesis of Random Copolymer Poly(MMA-r-MEBIm-TFSI)

The synthesis of poly(MMA-r-MEBIm-TFSI) (Scheme 1b) is similar to thatof poly(MMA-b-MEBIm-TFSI) described above (Scheme 1a). Yield: 0.380 g ofsolid particles (70.1%). ¹H NMR (500 MHz, DMSO-d₆, 23° C.) δ (ppm): 9.26(s, 1H, N—CH═N), 7.86-7.82 (d, 2H, N—CH═CH—N), 4.50-4.22 (d, 6H,N—CH₂—CH₂—O, N—CH₂—CH₂—CH₂), 3.54 (s, 3H, OCH₃), 1.80-1.73 (d, 4H,CH₂—C(CH₃), N—CH₂—CH₂—CH₂—CH₃), 1.31 (s, 5H, N—CH₂—CH₂—CH₂—CH₃,CH₂—C(CH₃)), 0.92 (s, 6H, N—CH₂—CH₂—CH₂—CH₃, CH₂—C(CH₃)), 0.73-0.55 (d,3H, CH₂—C(CH₃)). Elemental Anal. Calcd: C, 49.37; H, 6.40; N, 3.42; F,9.28; S, 5.22; Br, 0.00. Found: C, 48.84; H, 6.39; N, 3.36; F, 9.38; S,4.96; Br, 0.00.

Example 1.2.6

Similar structures with extended tether lengths were analogouslyprepared according to Schemes 2-4.

Example 1.3 Solvent-Casting PIL Block and Random Copolymers

Polymers were dissolved in anhydrous acetonitrile (9% w/w) and cast ontoTeflon substrates (ca. 35 mm (L)×4 mm (W)×0.525 mm (T)). The polymersolution was partially covered and the solvent was allowed to evaporateunder ambient conditions for ca. 12 h. Polymer films were subsequentlyannealed under vacuum at 150° C. for 72 h. These annealed films wereused to characterize thermal, morphological and ion conductiveproperties. The film thicknesses, ranging between 100 to 200 μm, weremeasured with a Mitutoyo digital micrometer with ±0.001 mm accuracy.

Example 1.4 Characterization

All chemical structures, PIL compositions, and number-average molecularweights were characterized by ¹H NMR spectroscopy using a Varian 500 MHzspectrometer at 23° C. with DMSO-d₆ as the solvent. The chemical shiftswere referenced to tetramethylsilane (TMS). The efficacy of ion exchangein PIL block and random copolymers was confirmed by elemental analysis(Atlantic Microlab, Inc., Norcross, Ga.). The molecular weights andmolecular weight distributions of PMMA macro-CTA and PIL block andrandom copolymers were determined by size exclusion chromatography (SEC)using a Waters GPC system equipped with two DMF Styragel columns(Styragel™HR 3 and Styragel™HR 4, effective separation of molecularweight ranges: 500-30,000 and 5,000-600,000) and a 2414 reflective index(RI) detector. All measurements were performed at 40° C. A mixture ofDMF and 0.05 M LiBr was used as a mobile phase at a flowrate of 1.0ml/min. Polyethylene glycol/polyethylene oxide (PEG/PEO) standards(Fluka) with molecular weights ranging from 628 to 478000 g mol⁻¹ wereused for calibration.

The PIL block copolymer precursors were prepared by sequential additionof monomers. A single batch of PMMA macro-chain transfer agent(macro-CTA) was first synthesized by RAFT polymerization using4-cyano-4-(phenylcarbonothioylthio)pentanoic acid as the CTA.Subsequently, a series of PIL diblock copolymer precursors(poly(MMA-b-MEBIm-Br)) with various PIL compositions (see Table 1) wereprepared via a chain extension reaction of the PMMA macro-CTA (Scheme1a). Typical SEC results (see Table 1A), shown in FIG. 1, clearlyindicate an increase in molecular weight from the PMMA macro-CTA(M_(n)=12.53 kg mol⁻¹) to a PIL block copolymer precursor(poly(MMA-b-MEBIm-Br-13.3), 13.3 mol % of PIL, M_(n)=22.93 kg mol⁻¹),and relatively low polydispersities for the PMMA macro-CTA(M_(w)/M_(n)=1.19) and the PIL block copolymer precursor(M_(w)/M_(n)=1.31) compared to the PIL random copolymer precursor(M_(w)/M_(n)=2.28) at a similar PIL composition(poly(MMA-r-MEBIm-Br-12.7), 12.7 mol % of PIL, M_(n)=29.83 kg mol⁻¹).The M_(n) of PMMA macro-CTA measured by SEC is in good agreement withthe result calculated from the ¹H NMR spectrum (M_(n)=13.1 kg mol⁻¹,FIG. 2 a). The successful chain extension reaction was also evidenced bythe incorporation of the MEBIm-Br IL monomer, i.e., the appearance ofprotons at C(2) (9.82 ppm) and C(4,5) (8.02 ppm) from the imidazoliumring in ¹H NMR spectrum (FIG. 2 b). The anion exchange from Br anion toTFSI anion was evidenced by the chemical shifts of C(2) and C(4,5)protons to 9.24 ppm and 7.83-7.75 ppm, respectively. Elemental analysisfurther confirmed that there was no residual bromide anion present inthe resulting polymers and the measured results were in a good agreementwith theoretical values (see Table 2).

A series of PIL random copolymer precursors were synthesized using AIBNas an initiator. Six samples of poly(MMA-r-MEBIm-Br) with similar PILcompositions as the PIL block copolymers ranging from 3.9 mol % to 15.4mol % were selected for anion exchange to TFSI counterion form. The PILcompositions for both PIL block and random copolymers are listed inTable 3.

TABLE 1A Reaction Conditions, Molecular Weight of PIL Block and RandomCopolymer Precursors. PIL Block Copolymer Precursors^(a) mol %Recipe^(b) M_(n) (kg mol⁻¹)^(d) M_(n)(kg mol⁻¹)^(e) PDI^(e)Poly(MMA-b-MEBIm-Br-3.9) 3.9 10:1:0.1 13.1 + 1.7  17.21 1.22Poly(MMA-b-MEBIm-Br-6.6) 6.6 20:1:0.1 13.1 + 2.94 18.23 1.22Poly(MMA-b-MEBIm-Br-9.5) 9.5 30:1:0.1 13.1 + 4.36 19.45 1.33Poly(MMA-b-MEBIm-Br-11.9) 11.9 40:1:0.1 13.1 + 5.6  20.38 1.41Poly(MMA-b-MEBIm-Br-13.3) 13.3 50:1:0.1 13.1 + 6.39 22.93 1.31Poly(MMA-b-MEBIm-Br-15.4) 15.4 60:1:0.1 13.1 + 7.55 23.18 1.60 PILRandom Copolymer Precursors^(a) mol % Recipe^(c) M_(n)(kg mol⁻¹)M_(n)(kg mol⁻¹)^(e) PDI^(e) Poly(MMA-r-MEBIm-Br- 3.1 19:1  — 20.13 2.053.1) Poly(MMA-r-MEBIm-Br- 4.8 12:1  — 25.84 2.03 4.8)Poly(MMA-r-MEBIm-Br- 6.8 9:1 — 23.5 2.32 6.8) Poly(MMA-r-MEBIm-Br-12.3)12.3 4.8:1   — 25.33 2.33 Poly(MMA-r-MEBIm-Br-12.7) 12.7 4.5:1   — 29.832.28 Poly(MMA-r-MEBIm-Br-15.3) 15.3 4:1 — 23.17 2.10 ^(a)b = blockcopolymer, r = random copolymer, Br = bromide counterion, number standsfor the PIL composition in mol %, which was determined from ¹H NMRspectra of copolymer PILs; ^(b)A:B:C = MEBIm-Br:PMMA-CTA:AIBN (in mol);^(c)A:B = MMA:MEBIm-Br (in mol); ^(d)Calculated from ¹H NMR spectrum ofPMMA macro-CTA and chemical structures of PIL block copolymer PILs;^(e)Determined by SEC.

TABLE 1B Reaction Conditions, Molecular Weight of Neutral BlockCopolymer Precursors and Homopolymer Precursor Neutral Block Copolymerand Homopolymer Precursors^(a) mol % Recipe^(b) M_(n) (kg mol⁻¹)^(c)M_(n) (kg mol⁻¹)^(d) PDI^(d) Poly(MMA-b-BrUMA-5.4) 5.4 10:1:0.1 19.8 +3.4  22.52 1.19 Poly(MMA-b-BrUMA-12.3) 12.3 35:1:0.1 19.8 + 7.76 26.451.26 Poly(MMA-b-BrUMA-17.3) 17.3 50:1:0.1 19.8 + 10.9 27.51 1.33Poly(MMA-b-BrUMA-20.3) 20.3 60:1:0.1 19.8 + 12.8 30.42 1.38Poly(MMA-b-BrUMA-23.3) 23.3 100:1:0.1 19.8 + 14.7 28.43 1.48Poly(MMA-b-BrUMA-37.9) 37.9 150:1:0.1 19.8 + 23.9 31.26 1.46 Poly(BrUMA)100 20:0:0.1 — 43.27 4.28 ^(a)b = block copolymer, Br = bromidecounterion, number stands for BrUDA composition in mole %, which wasdetermined from ¹H NMR spectra of copolymers; ^(b)A:B:C =BrMUA:PMMA-CTA:AIBN (in mol); ^(c)Calculated from ¹H NMR spectrum ofPMMA macro-CTA and chemical structures of BrMUDA block copolymers;^(d)Determined by size exclusion chromotography.

TABLE 1C PIL Block Copolymers and Homopolymer T_(g) Sample Name^(a) mol% wt. % vol %^(b) (° C.)^(c) IEC^(d) Poly(MMA-b-MUBIm-Br- 5.4 20.1621.46 131 0.47 5.4) Poly(MMA-b-MUBIm-Br- 12.3 38.29 40.17 23, 124 0.9112.3) Poly(MMA-b-MUBIm-Br- 17.3 48.07 50.05 24, 125 1.15 17.3)Poly(MMA-b-MUBIm-Br- 20.3 52.99 54.95 26, 127 1.28 20.3)Poly(MMA-b-MUBIm-Br- 23.3 57.34 59.26 27, 125 1.39 23.3)Poly(MMA-b-MUBIm-Br- 37.9 72.98 74.51 23, 124 1.81 37.9)Poly(MUBIm-Br)^(e) 100 100 100 −14 2.58 ^(a)Numbers correspond to PILmol %, which was determined from ¹H NMR spectroscopy. ^(b)Volumefractions calculated from density of PMMA (1.18 g cm⁻³) and PILhomopolymer (1.09 g cm⁻³). ^(c)Determined from differential scanningcalorimetry using the midpoint method. ^(d)Calculated as mmol Im⁺ per gof polymer. ^(e) PIL homopolymer.

Table 2 shows the elemental analysis results of PIL block(poly(MMA-b-MEBIm-TFSI)) and random (poly(MMA-r-MEBIm-TFSI)) copolymers.These block and random copolymers were synthesized via anion exchangereactions with their block (poly(MMA-b-MEBIm-Br)) and random(poly(MMA-r-MEBIm-Br)) copolymer precursors accordingly. Negligibleamount of Br was found in the resulting TFSI anion exchanged PIL blockand random copolymers.

TABLE 2 Elemental Analysis of PIL Block and Random Copolymers with TFSIas Counteranion. wt % C H N F S Br PIL Block Copolymer Poly(MMA-b- Calc.55.27 7.33 1.52 4.11 2.31 0 MEBIm-TFSI-4.3) (%) Exp. 54.71 7.23 1.353.02 1.83 trace^(a) (%) Poly(MMA-b- Calc. 52.89 6.95 2.29 6.20 3.49 0MEBIm-TFSI-7.1) (%) Exp. 52.26 6.76 2.31 6.01 3.41 0.46 (%) Poly(MMA-b-Calc. 51.98 6.81 2.58 6.99 3.93 0 MEBIm-TFSI-8.3) (%) Exp. 50.67 6.582.90 7.72 4.22 trace  (%) Poly(MMA-b- Calc. 49.39 6.40 3.42 9.26 5.21 0MEBIm-TFSI-12.3) (%) Exp. 48.84 6.25 3.41 9.07 4.94 trace  (%)Poly(MMA-b- Calc. 48.78 6.30 3.61 9.79 5.51 0 MEBIm-TFSI-13.4) (%) Exp.47.09 5.96 4.01 10.66 5.97 trace  (%) Poly(MMA-b- Calc. 47.64 6.12 3.9810.8 6.07 0 MEBIm-TFSI-15.7) (%) Exp. 44.90 5.63 4.39 11.98 6.56 0.53(%) PIL Random Copolymer Poly(MMA-r- Calc. 55.84 7.42 1.33 3.62 2.03 0MEBIm-TFSI-3.7) (%) Exp. 55.40 7.25 1.37 3.50 2.06 0 (%) Poly(MMA-r-Calc. 53.19 7.00 2.19 5.94 3.34 0 MEBIm-TFSI-6.7) (%) Exp. 52.56 7.012.27 5.95 3.42 0 (%) Poly(MMA-r- Calc. 49.37 6.4 3.42 9.28 5.22 0MEBIm-TFSI-12.3) (%) Exp. 48.84 6.39 3.36 9.38 4.96 0 (%) Poly(MMA-r-Calc. 47.80 6.15 3.93 10.66 6.00 0 MEBIm-TFSI-15.4) (%) Exp. 47.73 6.193.81 10.34 5.46 0 (%) ^(a)trace < 0.25 wt %.

The density of the PIL homopolymer (poly(MEBIm-TFSI)) was estimated froman additive contribution of components to the molar volume, which isanalogous to the group contribution method, where the polymer density isestimated from the additive contribution of functional groups. In otherwords, the chemical structure of poly(MEBIm-TFSI) can be divided intotwo components: poly(methyl methacrylate) (PMMA) and tethered TFSI ionicpart (i.e., 1-methyl-3-butylimidazoliumbis(trifluoromethanesulfonyl)imide, MBIm-TFSI):

Thus, the total molar volume (cm³ mol⁻¹) of poly(MEBIm-TFSI) can beexpressed as the addition of the molar volumes of these two components:

$\begin{matrix}{\frac{M}{\rho} = {\frac{M_{PMMA}}{\rho_{PMMA}} + \frac{M_{IL}}{\rho_{IL}}}} & (1)\end{matrix}$where M, M_(PMMA), M_(IL) and ρ, ρ_(PMMA), ρ_(IL) are the molecularweights (g mol⁻¹) and densities (g cm⁻³) of the PIL, PMMA and theMBIm-TFSI ionic liquid (IL), respectively. Normalizing Eq. 1 by thetotal molecular weight yields:

$\begin{matrix}{\frac{1}{\rho} = {\frac{w_{PMMA}}{\rho_{PMMA}} + \frac{w_{IL}}{\rho_{IL}}}} & (2)\end{matrix}$From Eq. 1, the PIL density can be determined from the experimentaldensities of PMMA (ρ_(PMMA)=1.18 g cm⁻³) and MBIm-TFSI IL (ρ_(IL)=1.42 gcm⁻³) and the weight fractions of PMMA (w_(PMMA)=0.193) and IL(w_(IL)=0.807), which were calculated from the chemical structure. Thus,the calculated density for PIL poly(MEBIm-TFSI) is 1.37 g cm⁻³. In thisstudy, we also assume that the variation of volume fraction due to thedensity change at different temperatures is negligible for these PILblock and random copolymers.

Example 1.5 Thermal Properties

Glass transition temperatures (T_(g)s) were determined by differentialscanning calorimetry (DSC; TA Instruments, Q200) over a temperaturerange of −60° C. to 180° C. at a heating/cooling rate of 10° C./minunder N₂ environment using a heat/cool/heat method. T_(g) was determinedusing the mid-point method from the second thermogram heating cycle.Thermal degradation temperatures (T_(d)s) were by measured thermalgravimetric analysis (TGA; TA Instruments, Q50) over a temperature rangeof 30° C. to 800° C. at a heating rate of 10° C./min under N₂environment. T_(d) was reported at 5% weight loss of a polymer sample.

FIG. 3 shows glass transition temperatures (T_(g)s) of the PIL block andrandom copolymers containing TFSI counterions as a function of PILcomposition, where both sets are compared to a PMMA homopolymer controlsample (0 mole % PIL). Note that the PMMA homopolymer control for thePIL block copolymers was synthesized by RAFT polymerization (i.e., PMMAmacro-CTA), while the other homopolymer control for the PIL randomcopolymer was synthesized by free radical polymerization. Also, notethat there was no difference in T_(g) for homopolymers synthesized byeither RAFT polymerization (FIG. 3A) or free radical polymerization(FIG. 3B). For the PIL random copolymers with TFSI counterions (FIG.3B), there is only one relatively narrow T_(g), which decreases from124° C. to 93° C. with increasing PIL composition from 0 to 15.4 mol %.This reduction in T_(g) can be attributed to the lower T_(g) of the PIL(poly(MEBIm-TFSI), T_(g)=7° C.), where the TFSI counterion reduces thePIL T_(g) compared to the Br counterion due to the plasticization effectof the bulky TFSI anion with its lower symmetry, extensive chargedelocalization, and the higher flexibility. In contrast, two broaderglass transitions were observed for PIL block copolymers with TFSIcounterions at most PIL compositions (FIG. 3A. Two distinct T_(g)s areexpected for microphase-separated block copolymers. Specifically, forstrongly microphase-separated block copolymers, the T_(g)s for eachblock typically do not change with changing block composition. However,FIG. 3A shows that the T_(g)s for both the PIL and PMMA blocks deviatesignificantly with changing block composition compared to the purehomopolymer T_(g)s, (poly(MEBIm-TFSI), T_(g)=7° C.; PMMA, T_(g)=124°C.). More specifically, the PIL block T_(g) increases from 7 to 85° C.from 100 to 7.1 mole % PIL composition, while the PMMA block T_(g)decreases from 124 to 106° C. from 0 to 15.7 mole % PIL composition.Also, note that only one glass transition was observed in FIG. 3A at 4.3mol % PIL composition, which may be due to relatively short length ofthe PIL block at this low PIL composition. Overall, the data in FIG. 3Asuggests that there is microphase separation in these PIL blockcopolymers as evidenced by two distinct T_(g)s, but that this separationis weak as evidenced by the significant deviation in T_(g)s of bothblocks with changing PIL composition. Note that the number-averagemolecular weight of the PMMA macro-CTA was 13.1 kg mol⁻¹, while that ofthe PIL block ranged from 3-12.6 kg mol⁻¹ (calculated from the moleratio of a PMMA block to a PIL block determined by NMR) for the PILcomposition range we studied. This indicates that the deviation ofT_(g)s is less likely attributed to a relatively low molecular weight ofthe PIL block. Thus, the T_(g) deviation and the effect of PILcomposition on both T_(g)s may be attributed to the partially compatiblenature of the methacrylate-based TFSI PIL block and the PMMA block. Itis worthwhile to note that PMMA is miscible with the analogous smallmolecule TFSI ionic liquid that is covalently attached in the PIL block(e.g., 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide(EMIm-TFSI)), suggesting that there may be a partial affinity betweenthe PIL block and PMMA block in this PIL block copolymer. A similarbehavior of T_(g) deviation was also reported in literature for blockcopolymers of poly(ethylene oxide) and PMMA, which was attributed to anintramolecular plasticizing effect.

FIG. 3C shows T_(g)s of PIL block and random copolymers as a function ofPIL composition. As expected, the one T_(g) of PIL random copolymerdecreases with increasing PIL composition and lies between the T_(g) ofthe PMMA (T_(g,1)) and PIL (T_(g,2)) blocks of the PIL block copolymer.A comparison of the T_(g)s of the PIL random copolymers to theGordon-Taylor equation is shown in FIG. 4. The Gordon-Taylor equationhas one empirical fitting parameter:

$\begin{matrix}{T_{g} = \frac{{w_{1}T_{g,1}} + {{Kw}_{2}T_{g,2}}}{w_{1} + {Kw}_{2}}} & (1)\end{matrix}$where w₁ and w₂ are weight fractions of the two components, and K is thefitting parameter. If K=T_(g,1)/T_(g,2), the Gordon-Taylor equationsimplifies to the Fox equation, a well-known equation that can describea fully miscible system. FIG. 3C indicates that the T_(g) of randomcopolymers can be well described by the Gordon-Taylor equation withK=0.37 (the best fit). Note that this value is far different fromT_(g,1)/T_(g,2)=1.42, indicating that the IL monomeric units are notfully mixed with the MMA monomeric units. Clearly, FIG. 3C furtherindicates T_(g)s of PMMA block and the PIL block in block copolymerssignificantly deviate from their homopolymers (PMMA and PIL), suggestingthat PIL is not fully immiscible with PMMA. The glass transitionanalysis suggests that the PIL block and PMMA block are partiallymiscible in these PIL block copolymers.

In contrast with the trends in T_(g), the TGA thermograms (see FIG. 3D)show that there is no significant difference in thermal degradationtemperature (T_(d), determined by 5 wt % loss) between these PIL blockand random copolymers.

For these PIL block copolymers, T_(d) slightly increases from 257-284°C. (Table 3) with increasing PIL composition from 4 to 15.7 mol %, whilethere is almost negligible change in T_(d) (ca. 260° C.) (Table 3) forPIL random copolymers. This slight increase in T_(d) in these PIL blockand random copolymers compared with their PMMA homopolymers is due tothe higher T_(d) of the MEBIm-TFSI block (T_(d)=363° C.). Note that theT_(d)s for PMMA macro-CTA synthesized by RAFT polymerization and PMMAhomopolymer synthesized by free radical polymerization are 260° C. and250° C., respectively.

TABLE 3 Thermal Properties of PIL Block and Random Copolymers with TFSIas Counteranion. mol T_(g) % vol %^(b) T_(d) (° C.)^(c) (° C.)^(d) PILBlock Copolymers^(a) Poly(MMA-b-MEBIm-TFSI-4.3) 4.3 16.5 257 121Poly(MMA-b-MEBIm-TFSI-7.1) 7.1 25.2 270 85, 119Poly(MMA-b-MEBIm-TFSI-8.3) 8.3 28.6 276 78, 117Poly(MMA-b-MEBIm-TFSI-12.3) 12.3 38.5 277 62, 116Poly(MMA-b-MEBIm-TFSI-13.4) 13.4 40.8 286 64, 109Poly(MMA-b-MEBIm-TFSI-15.7) 15.7 45.3 284 63, 106 PIL RandomCopolymers^(a) Poly(MMA-r-MEBIm-TFSI-3.7) 3.7 14.5 260 117Poly(MMA-r-MEBIm-TFSI-4.9) 4.9 18.6 263 114 Poly(MMA-r-MEBIm-TFSI-6.7)6.7 24.1 259 110 Poly(MMA-r-MEBIm-TFSI-12.3) 12.3 38.5 267 99Poly(MMA-r-MEBIm-TFSI-13.3) 13.3 40.7 265 98 Poly(MMA-r-MEBIm-TFSI-15.4)15.4 44.7 268 93 ^(a)Numbers correspond to PIL mole %, which wasdetermined from ¹H NMR spectroscopy; ^(b)Volume fractions calculatedfrom density of PMMA (1.18 g cm⁻³) and PIL homopolymers (1.37 g cm⁻³,see Supporting Information); ^(c)Determined at 5% weight loss;^(d)Determined by mid-point method.

Example 1.6 Morphology

Small angle X-ray scattering (SAXS) was performed on PIL block andrandom copolymer samples both through and in the plane of the films. TheCu X-ray was generated from a Nonius FR 591 rotating-anode generatoroperated at 40 kV and 85 mA. The bright, highly collimated beam wasobtained via Osmic Max-Flux optics and pinhole collimation in anintegral vacuum system. The SAXS and WAXS scattering data were collectedusing a Bruker Hi-Star two-dimensional detector at a sample-to-detectordistance of 150 cm and 11 cm, respectively. Using the Datasqueezesoftware, isotropic 2-D scattering patterns were converted to 1-D plotsusing azimuthal angle integration (0-360°). The scattering intensity wasfirst corrected for the primary beam intensity, and then the backgroundscattering from an empty cell was subtracted for correction.Morphologies were also studied using a JEOL 2010F transmission electronmicroscope (TEM) operating at 200 kV. PIL block copolymer samples weresectioned at room temperature using a Reichert-Jung ultra-microtome witha diamond knife. Polymer samples with ultrathin sections of ca. 40-60 nmnominal thickness were collected on copper grids for examination. Theinterdomain distance in the TEM was determined from fast Fouriertransforms (FFTs) produced by Gatan Digital Micrograph™ (DM) software.

FIG. 4 shows through-plane SAXS profiles for both PIL block and randomcopolymers with TFSI counteranions. The scattering profiles (FIG. 4A) ofthese PIL block copolymers at PIL compositions from 4.3 to 15.7 mol %show one broad primary scattering peak. This one peak is indicative of amicrophase-separated morphology; however, the lack of multiplereflections suggests that there is no long-range periodicity and thatthe two blocks are not strongly microphase separated. This is in goodagreement with the T_(g) trends observed for both blocks as a functionof PIL composition (FIG. 3A). Additionally, the peak position (q*)decreases from 0.42 to 0.30 nm⁻¹ with increasing PIL composition, exceptfor PIL block copolymer at a PIL composition of 13.4 mol %. Thisdecrease in peak location corresponds to an increase in interdomaindistance from ca. 15 to 21 nm with increasing PIL composition ascalculated by 2π/q*. It should be also noted that there was nodifference in scattering patterns between in-plane (see FIG. 5A) andthrough-plane scattering profiles (FIG. 4A), indicating an isotropicmorphology in these PIL block copolymers at all PIL compositions.Temperature-dependent X-ray scattering indicates that there is no changein morphology type for the temperature range of 30 to 150° C. (see FIG.5B). In contrast to the PIL block copolymers, the scattering profile ofthe PIL random copolymer at 15.4 mole % PIL composition in FIG. 4B showsa featureless decay with increasing q as is consistent with the absenceof microphase separation. PIL random copolymers at other PILcompositions show similar SAXS patterns (data not shown). This datacorroborates with the one T_(g) observed in the PIL random copolymers(FIG. 3B).

FIG. 6 shows a TEM image of the PIL block copolymer with 13.4 mole %PIL. The TEM image clearly indicates a microphase-separated morphologywith no long-range periodic order, which is consistent with the DSC andSAXS results. The measured interdomain distance is in the range of 12 to15 nm, which is slightly smaller than the results obtained from SAXS(ca. 18 nm) for the 13.4 mole % PIL block copolymer. This discrepancycould be the consequence of compression during microtomy.

Example 1.7 Ionic Conductivity

The ionic conductivities of polymer films were measured withelectrochemical impedance spectroscopy (EIS; Solartron, 1260 impedanceanalyzer, 1287 electrochemical interface, Zplot software) over afrequency range of 1 Hz to 10⁶ Hz at 200 mV. Conductivities werecollected in an environmental chamber (Tenney, BTRS model), wheretemperature and relative humidity (<10% RH) were controlled. Thein-plane conductivities of the PIL films were measured in a cell withfour-parallel electrodes, where an alternating current was applied tothe outer electrodes and the real impedance or resistance, R, wasmeasured between the two inner reference electrodes. The resistance wasdetermined from a high x-intercept of the semi-circle regression of theNyquist plot. Conductivity was calculated by using the followingequation: σ=L/AR, where L and A are the distance between two innerelectrodes and the cross sectional area of the polymer film (A=Wl; W isthe film width and l is the film thickness), respectively. Samples wereallowed to equilibrate for 2 h at each temperature at <10% RH followedby 6 measurements at the equilibrium condition. The values reported arean average of these steady-state measurements.

FIG. 7 shows a comparison of temperature-dependent ionic conductivity ofthe PIL block and random copolymers bearing TFSI counteranions at acomparable PIL composition. Surprisingly, the ionic conductivities ofthis PIL block copolymer are ca. 2 orders of magnitude higher than thatof this PIL random copolymer at all temperatures investigated. A similarca. 2 orders of magnitude difference was observed for these PIL blockand random copolymers at other PIL compositions ranging from ca. 7 to 15mole % (see FIG. 8). This difference is further illustrated in FIG. 9where the ionic conductivities of the PIL block and random copolymersare plotted as a function of PIL composition (vol %) at a fixedtemperature (150° C.).

For polymer electrolytes, ionic conductivity is strongly dependent onpolymer segmental relaxation and the local concentration of conductingions (i.e., dissociated ions). The fact that ionic conductivityprimarily depends on T_(g) is due to the coupling of ion motion withpolymer segmental dynamics. Thus, one would expect a difference inconductivity when comparing a strongly microphase-separated ionic blockcopolymer to that of an ionic random copolymer due to the significantlylower T_(g) in the ionic block microdomains of the block copolymercompared to the higher T_(g) in the homogeneous random copolymer.However, in this case, the weakly microphase-separated PIL blockcopolymers have slightly lower T_(g)s in the PIL block (e.g., 63° C. at15.7 mole % PIL) compared to the PIL random copolymers (e.g., 93° C. at15.4 mole % PIL). Therefore, it is surprising that a relatively modestdifference in T_(g) produces an increase in ionic conductivity of ca. 2orders of magnitude. For comparison, this PIL homopolymer with differentcounter ions of similar size resulted in differences in T_(g) of 35° C.,but produced only modest differences in conductivity.

Another factor that affects ion transport in a solid-state polymerelectrolyte is the local concentration of conducting ions. In comparisonwith a random copolymer where TFSI anions are homogeneously distributed,a block copolymer has a much higher local ion concentration even at thesame overall PIL composition, which can be attributed to localconfinement of conducting ions in the microphase-separated ionicdomains. The increase in ionic conductivity due to a favorablyconcentrated distribution of ions was recently reported in the mixtureof poly(styrene-b-ethylene oxide) block copolymers and LiTFSI where thesalt is increasingly localized in the poly(ethylene oxide) block withincreasing molecular weight of the block copolymer. Similarly, due tothe effect of nanodomain confinement, in the mixture ofproton-conducting IL with PS-b-P2VP, an ion diffusion enhancement wasobserved compared to the mixture of IL with P2VP homopolymer. Note thatthese salt or ionic liquid-doped block copolymers exhibit lamellarstructures and mobile cations and anions, while the single anionconductor PIL block copolymers in this study exhibited a weakmicrophase-separated morphology without periodic long-range order. Thisindicated that the local confinement of conducting ions greatlyfacilitated ion transport and significantly contributed to an increasein ionic conductivity even for a block copolymer with weaklymicrophase-separated morphology. Without being bound by the correctnessof any given theory, this phenomenon can be attributed to the increasein local ion concentration that shortened the ion hopping distance andinduces faster ion transport in the nanoscale ionic domains of blockcopolymers.

Example 1.8 General Remarks

A series of polymerized ionic liquid (PIL) block and random copolymerswere synthesized from an ionic liquid monomer,1-[(2-methacryloyloxy)ethyl]-3-butylimidazoliumbis(trifluoromethanesulfonyl)imide (MEBIm-TFSI), and a non-ionicmonomer, methyl methacrylate (MMA), at various PIL compositions with thegoal of understanding the influence of morphology on ion transport. Forthe diblock copolymers, the partial affinity between the PIL and PMMAblocks resulted in a weakly microphase-separated morphology with noevident long-range periodic structure across the PIL composition rangestudied, while the random copolymers revealed no microphase separation.These morphologies were identified with a combination of techniques,including differential scanning calorimetry, small angle X-rayscattering, and transmission electron microscopy. Surprisingly, atsimilar PIL compositions, the ionic conductivity of the block copolymerswere ca. 2 orders of magnitude higher than the random copolymers despitethe weak microphase-separated morphology evidenced in the blockcopolymers. The higher conductivity in the block copolymers wasattributed to its microphase-separated morphology, because thedifference in glass transition temperature between the block and randomcopolymers is insignificant. Therefore, this work demonstrated thatlocal confinement of conducting ions in nanoscale ionic domains in PILblock copolymers can accelerate ion transport significantly.

Example 2 Effect of Nanostructured Morphology on Ion Transport inPolymerized Ionic Liquid Block Copolymers

In this study, a series of strongly microphase-separated polymerizedionic liquid (PIL) diblock copolymers,poly(styrene-b-1((2-acryloyloxy)ethyl)-3-butylimidazoliumbis(trifluoromethanesulfonyl)imide) (poly(S-b-AEBIm-TFSI)), weresynthesized to explore relationships between morphology and ionicconductivity. Using small-angle X-ray scattering and transmissionelectron microscopy, a variety of self-assembled nanostructuresincluding hexagonally packed cylinders, lamellae, and coexistinglamellae and network morphologies were observed by varying PILcomposition (6.6-23.6 PIL mol %). At comparable PIL composition, thisacrylate-based PIL block copolymer with strong microphase separationexhibited ˜1.5-2 orders of magnitude higher ionic conductivity than amethacrylate-based PIL block copolymer with weak microphase separation.Remarkably, high ionic conductivity (0.88 mS cm−1 at 150° C.) and amorphology factor (normalized ionic conductivity, f) of ˜1 was achievedthrough the morphological transition from lamellar to a coexistence oflamellar and three-dimensional network morphologies with increasing PILcomposition in anhydrous single-ion conducting PIL block copolymers,which highlights a good agreement with the model predictions. Inaddition to strong microphase separation and the connectivity ofconducting microdomains, the orientation of conducting microdomains andthe compatibility between polymer backbone and IL moiety of PIL alsosignificantly affect the ionic conductivity. This study provides avenuesto controlling the extent of microphase separation, morphology, and iontransport properties in PIL block copolymers for energy conversion andstorage applications.

Example 2.1 Materials

Acryloyl chloride (97%, contains <210 ppm monomethyl ether hydroquinone(MEHQ) as stabilizer), 2-bromoethanol (95%), triethylamine (≧99.5%),dichloromethane (≧99.5%), potassium bicarbonate (KHCO3, 99.7%),magnesium sulfate (anhydrous, 99%), calcium hydride (CaH₂, 95%),4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid (chaintransfer agent (CTA), >97%, HPLC), tetrahydrofuran (THF, ≧99.9%, HPLC),methanol (99.8%), 1-butylimidazole (98%), N,N-dimethylformamide (DMF,99.9%, HPLC), hexanes (≧98.5%), lithiumbis(trifluoromethanesulfonyl)imide (LiTFSI, 97%), acetonitrile(anhydrous, 99.8%), deuterated chloroform (CDCl₃, 99.96 atom % D,contains 0.03% v/v TMS), and dimethyl-d6 sulfoxide (DMSO-d6, 99.9 atom %D, contains 0.03% v/v TMS) were used as received from Sigma-Aldrich.Azobis(isobutyronitrile) (AIBN, 98%, Sigma-Aldrich) was purified byrecrystallization twice from methanol. Styrene (S, 99%, Sigma-Aldrich)was purified by distillation over CaH2 at a reduced pressure. Ultrapuredeionized (DI) water with resistivity ca. 16 MΩ cm was used asappropriate.

Example 2.2 Syntheses

A series of acrylate-based PIL block copolymers with various PILcompositions were synthesized via the following route: sequential RAFTpolymerization, quaternization reaction, and anion exchange reaction.Overall, the synthesis route was similar that described in Example 1. Amajor difference is that the imidazolium moiety was not introduced inthe stage of monomer synthesis (Scheme 5), but in the polymer stage(Scheme 6). The advantage of this synthesis route was that itfacilitates the modular synthesis of a series of PIL block copolymers atconstant average degree of polymerization and molecular weightdistribution with varied structures and functionalities, thus enablingan experimentalist to vary the physical properties by selectingdifferent PIL chemical structures. For the characterizations, thechemical structure was analyzed by ¹H NMR (see Example 2.4). Thecompositions shown in Table 4 were determined from relative integrationsof proton resonances of the imidazolium ring at C(4,5) (g, h) positionsversus the sum of all styrenic proton resonances at ortho (a), meta (b),and para positions (c). The molecular weight determined by SEC was inthe range from 9.95 to 18.80 kg mol−1 with polydispersity ranging from1.24 to 1.28. Note that the polydispersity was determined from theneutral block copolymer, poly(S-b-BrEA), before the quaternizationreaction. The efficacy of ion exchange from the Br anion form to TFSIanion form was confirmed by elemental analysis

Example 2.2.1 Synthesis of 2-Bromoethyl Acrylate (BrEA)

The synthesis of 2-bromoethyl acrylate (BrEA) monomer is shown in Scheme5. A typical experimental procedure is described as follows. To athree-neck 500 mL flask in an ice bath, the mixture of 37.47 g (0.3 mol)of 2-bromoethanol and 30 mL of dichloromethane solvent was charged intothe reactor. Under the nitrogen environment, the mixture of 30.66 g(0.303 mol) of triethylamine and 40 mL of dichloromethane was added intothe reactor, followed by slowly adding the mixture of 27.42 g (0.303mol) of acryloyl chloride and 30 mL of dichloromethane in the reactorthrough an addition funnel. After addition, the ice bath was removed.The reaction mixture was stirred at room temperature for 18 h, and thenthe white solid precipitants (a byproduct) were removed by filtration.The liquid filtrate was neutralized with KHCO₃ solution first and thenfurther stirred with 200 mL of DI water 4 times to completely driveresidual salt into the water layer. The water layer (byproduct) wasremoved by a separation funnel, and the residual water in the organiclayer was further removed using anhydrous magnesium sulfate. After theremoval of the dichloromethane solvent under vacuum, 38.57 g of theorganic liquid product BrEA was obtained (clear pale yellow liquid witha 71.8% yield). ¹H NMR (500 MHz, CDCl₃, 23° C.) δ (ppm): 6.51-6.45 (d,1H, HCH═CH), 6.22-6.12 (m, 1H, HCH═CH), 5.92-5.88 (d, 1H, HCH═CH),4.51-4.47 (m, 2H, O—CH₂—CH₂—Br), 3.59-3.55 (m, 2H, O—CH₂—CH₂—Br).

Example 2.2.2 Synthesis of PS Macro-CTA

The preparation of PS macro-chain transfer agent (macro-CTA) is shown inScheme 5(1). 34.55 g of S (0.332 mol) was mixed with 334.8 mg of CTA(0.829 mmol) in a 250 mL single-neck Schlenk flask. The flask wassubjected to four freeze-pump-thaw degassing cycles followed by sealingthe reactor and carrying out the reaction under static vacuum at 100° C.for 26 h. The resulting polymer was twice precipitated in methanol anddried under vacuum in an oven at room temperature for 24 h. Yield: 6.01g of solid particles (17.4%). ¹H NMR (500 MHz, CDCl₃, 23° C.) δ (ppm):7.22-6.28 (m, 5H, C₆H₅), 2.40-1.66 (m, 1H, CH2CH), 1.66-1.12 (m, 2H,CH₂CH); SEC (THF, 40° C.): Mn=7.54 kg mol−1, Mw/Mn=1.14 (against PSstandards).

Example 2.2.3 Synthesis of Diblock Copolymer Poly(S-b-BrEA)

The synthesis of the block copolymer (poly(S-b-BrEA)) is shown in Scheme5(2). A typical example is given as follows. 0.390 g of BrEA monomer(2.176 mmol), 0.328 g of PS macro-CTA (0.044 mmol), and 0.71 mg of AIBN(0.004 mmol) were mixed with 18 mL of THF solvent in a 50 mL Schlenkflask and subjected to four freeze-pump-thaw degassing cycles. Afterdegassing, the reactor was sealed, and the reaction was then carried outunder static vacuum at 55° C. for 6 h. The resulting copolymer was twiceprecipitated in methanol, filtered, and then dried under vacuum in anoven at 40° C. for 24 h. Yield: 0.359 g of solid particles (50.0%). ¹HNMR (500 MHz, CDCl₃, 23° C.) δ (ppm): 7.24-6.28 (m, 5H, C₆H₅), 4.40 (s,2H, —CH₂—CH₂—Br), 3.56 (s, 2H, O—CH₂—CH₂—Br), 2.60-1.66 (m, 1H, CH₂CH),1.66-0.70 (m, 2H, CH₂CH); SEC (THF, 40° C.): Mn=9.44 kg mol-1,Mw/Mn=1.26 (against PS standards).

Example 2.2.4 Synthesis of Diblock Copolymer Poly(S-b-AEBIm-Br)

The synthesis of poly(S-b-AEBIm-Br) was prepared by a quaternizationreaction (Scheme 6). A typical reaction process is given as follows.0.269 g of poly(S-b-BrEA-24) (0.518 mmol Br) and 0.321 g of1-butylimidazole (2.59 mmol) were mixed with 3 mL of DMF solvent in a 40mL vial, followed by stirring at 80° C. for 48 h. The reaction mixturewas three times precipitated in hexanes and extensively washed withhexanes. The resulting polymer was dried in a vacuum oven for 24 h.Yield: 0.303 g of solid particles (90.9%). ¹H NMR (500 MHz, DMSO-d₆, 23°C.) δ (ppm): 9.90 (s, 1H, N—CH═N), 8.08-7.95 (d, 2H, N—CH═CH—N),7.30-6.26 (m, 5H, C₆H₅), 4.80-4.05 (d, 4H, N—CH₂—CH₂—O,N—CH₂—CH₂—CH₂—CH₃), 3.56 (s, 4H, N—CH₂—CH₂—O, N—CH₂—CH₂—CH₂—CH₃),2.10-1.66 (m, 1H, CH₂CH), 1.66-1.10 (m, 2H, CH₂CH), 1.00-0.60 (m, 5H,N—CH₂—CH₂—CH₂—CH₃, N—CH₂—CH₂—CH₂—CH₃).

Example 2.2.5 Synthesis of Diblock Copolymer Poly(S-b-AEBIm-TFSI)

The anion exchange from poly(S-b-AEBIm-Br) to poly(S-b-AEBIm-TFSI) isshown in Scheme 5(4). In a typical procedure, poly(S-b-AEBIm-Br-24)(0.303 g, 0.464 mmol Br⁻) and LiTFSI (0.665 g, 2.319 mmol) were mixedwith DMF (3 mL) and then stirred at 50° C. for 24 h. The reactionmixture was twice precipitated into methanol/water (1/1 v/v) and washedextensively with DI water. The resulting polymer was filtered and driedunder vacuum in an oven at 40° C. for 24 h. Yield: 0.354 g of solidparticles (87.7%). ¹H NMR (500 MHz, DMSO-d₆, 23° C.) δ (ppm): 9.13 (s,1H, N—CH═N), 7.78-7.67 (d, 2H, N—CH═CH—N), 7.30-6.30 (m, 5H, C₆H₅),4.90-3.90 (m, 4H, N—CH₂—CH₂—O, N—CH₂—CH₂—CH₂—CH₃), 3.59 (s, 4H,N—CH₂—CH₂—O, N—CH₂—CH₂—CH₂—CH₃), 2.40-1.66 (m, 1H, CH₂CH), 1.66-1.10 (m,2H, CH₂CH), 1.00-0.70 (m, 5H, N—CH₂—CH₂—CH₂—CH₃, N—CH₂—CH₂—CH₂—CH₃).Elemental Analysis Anal. Calcd: C, 57.00; H, 5.39; N, 5.00; F, 13.56; S,7.63; Br, 0.00. Found: C, 55.58; H, 5.49; N, 4.86; F, 12.26; S, 7.39;Br, 0.00.

TABLE 4 Acrylate-Based PIL Block Copolymer Samples(Poly(S-b-AEBIm-TFSI)). mol wt vol M_(n) Sample^(a) % % %^(b) (kgmol⁻¹)^(c) PDI^(d) Morphology^(e) Poly(S-b-AEBIm-  6.6 24.2 18.3  9.951.24 C TFSI-6.6) Poly(S-b-AEBIm- 12.2 40.2 32.0 12.60 1.27 C TFSI-12.2)Poly(S-b-AEBIm- 17.0 49.8 41.0 15.00 1.28 L TFSI-17.0) Poly(S-b-AEBIm-23.6 59.9 51.1 18.80 1.26 L + G TFSI-23.6) ^(a)b = block copolymer, TFSI= bis(trifluoromethanesulfonyl)imide anion, numbers stand for PILcomposition in mol %, determined from ¹H NMR spectroscopy; ^(b)Volumefractions calculated from density of polystyrene (0.969 g cm⁻³) and PILhomopolymer (1.382 g cm⁻³, see Supporting Information); ^(c)Determinedfrom the molecular weight of poly(S-b-BrEA) (SEC), PIL composition (¹HNMR) and the chemical structure of poly(S-b-AEBIm-TFSI); ^(d)Taken fromthe polydispersity of poly(S-b-BrEA) (SEC); ^(e)Determined from X-rayand TEM, C = cylindrical, L = lamellar, G = gyroid. Note:poly(S-b-AEBIm-TFSI) =poly(styrene-block-1-((2-acryloyloxy)ethyl)-3-butylimidazoliumbis(trifluoromethanesulfonyl)imide)

Example 2.3 Solution-Casting PIL Block Copolymers

Block copolymers were dissolved in anhydrous acetonitrile (AcN) or THF(˜10% w/w) and cast onto Teflon substrates (ca. 35 mm (L)×4 mm (W)×0.525mm (H)). To investigate the effect of solvent evaporation on theresulting morphology and conductivity, the polymer solution was driedunder ambient conditions at two solvent evaporation rates: (1) fastdrying: partially covered and the solvent was allowed to evaporate inca. 12 h; (2) slow drying: a solvent reservoir was placed next to thecasting films, and the solvent was allowed to slowly evaporate over 120h. Subsequently, polymer films were further dried by placing in a fumehood and then annealed under vacuum at 150° C. for 72 h. Afterannealing, no residual solvent was detected in the films with FTIRATRspectroscopy (data not shown). These annealed films were used tocharacterize thermal, morphological, and ion conductive properties. Thefilm thicknesses, ranging between 100 and 200 μm, were measured with aMitutoyo digital micrometer with ±1 μm accuracy.

Example 2.4 Characterization

All chemical structures, PIL compositions, and number-average molecularweights were characterized by ¹H NMR spectroscopy using a Varian 500 MHzspectrometer at 23° C. with CDCl₃ or DMSO-d₆ as the solvent. (FIG. 10).The chemical shifts were referenced to tetramethylsilane (TMS). Theefficacy and purity of ion exchange in PIL block copolymers wereconfirmed by elemental analysis (Atlantic Microlab, Inc., Norcross,Ga.). Table 5.

TABLE 5 Elemental Analysis Results of Poly(S-b-AEBIm-TFSI).Styrene-Based PIL Block Copolymer wt % C H N F S Br Poly(S-b-AEBIm-Calc. (%) 78.00 6.80 2.02  5.48 3.08 0 TFSI-6.6) Exp. (%) 81.32 7.041.40  4.27 2.73 0 Poly(S-b-AEBIm- Calc. (%) 68.60 6.17 3.35  9.10 5.12 0TFSI-12.2) Exp. (%) 70.04 6.25 3.02  7.42 4.45 0 Poly(S-b-AEBIm- Calc.(%) 62.97 5.79 4.15 11.26 6.34 0 TFSI-17.0) Exp. (%) 63.10 5.85 4.0111.01 6.01 0 Poly(S-b-AEBIm- Calc. (%) 57.00 5.39 5.00 13.56 7.63 0TFSI-23.6) Exp. (%) 55.58 5.49 4.86 12.26 7.39 0

The density of poly(AEBIm-TFSI) homopolymer could be estimated using themethodology described in Example 1.4, above:

$\frac{1}{\rho} = {{\frac{w_{PMA}}{\rho_{PMA}} + \frac{w_{IL}}{\rho_{IL}}} = {\frac{0.169}{1.22} + \frac{0.831}{1.42}}}$ρ = 1.382

TABLE 6 PIL Block Copolymer Samples with similar PIL volume factions volT_(g,PIL) M_(n) Mor- Sample^(a) Name^(b) % ^(c) (° C.) (kg mol⁻¹) ^(d)PDI ^(d) phology^(e) BCP 1 Poly(S-b-AEBIm- 41.0 −7 15.00 1.28 LTFSI-17.0) BCP 2 Poly(S-b-VBHIm- 43.1 9 40.70 1.26 L TFSI-17.0) BCP 3Poly(MMA-b- 45.3 63 36.67 1.60 M MEBIm-TFSI- 15.7) ^(a)BCP = blockcopolymer; ^(b)Chemical structures of these block copolymers are shownabove; ^(c) Densities were calculated based on the volume additivity;^(d) Determined from SEC and their chemical structures; ^(e)Determinedfrom X-ray scattering profiles and TEM images: M = microphaseseparation.

The molecular weights and polydispersities of PS macro-CTA and PIL blockcopolymers were determined by size exclusion chromatography (SEC) usinga Waters GPC system equipped with a THF Styragel column (Styragel™HR 5E,effective separation of molecular weight range: 2-4000 kg mol-1) and a2414 reflective index (RI) detector. All measurements were performed at40° C. THF was used as a mobile phase at a flow rate of 1.0 mL/min. PSstandards (Shodex, Japan) with molecular weights ranging from 2.97 to197 kg mol⁻¹ were used to produce the molecular weight calibrationcurve. FIG. 12.

Glass transition temperatures (Tgs) were determined by differentialscanning calorimeter (DSC; TA Instruments, Q200) over a temperaturerange of −60 to 180° C. at a heating/cooling rate of 10° C./min under aN₂ environment using a heat/cool/heat method. Tg was determined usingthe midpoint method from the second thermogram heating cycle. See FIG.13.

Small-angle X-ray scattering (SAXS) was performed on PIL block copolymersamples both through and in the plane of the films. The Cu X-rays weregenerated by a Nonius FR 591 rotating-anode generator operated at 40 kVand 85 mA. The bright, highly collimated beam was obtained via OsmicMax-Flux optics and pinhole collimation in an integral vacuum system.The scattering data were collected using a Bruker Hi-Startwo-dimensional detector at a sample-to-detector distance of 150 cm.Using the Datasqueeze software, 32 isotropic 2-D scattering patternswere converted to 1-D plots using azimuthal angle integration(0-360°).The scattering intensity was first corrected for the primary beamintensity, and then the background scattering from an empty cell wassubtracted for correction. See FIG. 14-15.

Morphologies were also studied using a JEOL 2010F transmission electronmicroscope (TEM) operating at 200 kV. Poly(S-b-AEBIm-TFSI) PIL blockcopolymer samples were sectioned using a Reichert-Jung ultramicrotomewith a diamond knife at −70° C. Polymer samples with ultrathin sectionsof 40-60 nm nominal thickness were collected on copper grids forexamination. The TEM specimens for poly(S-b-AEBIm-TFSI) block copolymerswere stained with ruthenium tetroxide (RuO₄) vapor, and the PIL blockwas preferentially stained. The interdomain distance in the TEM wasdetermined from fast Fourier transforms (FFTs) produced by Gatan DigitalMicrograph (DM) and ImageJ software.

The ionic conductivities of polymer films were measured withelectrochemical impedance spectroscopy (EIS; Solartron, 1260 impedanceanalyzer, 1287 electrochemical interface, Zplot software) over afrequency range of 1-10⁶ Hz at 200 mV. Conductivities were collected inan environmental chamber (Tenney, BTRS model), where temperature andrelative humidity (<10% RH) were controlled. Previous results have shownthat conductivities measured under these conditions are comparable toconductivities measured in a glove/drybox by others for Im-TFSI ionicliquids, Im-TFSI ionic liquid monomers, and Im-TFSI polymers. Thein-plane conductivities of the PIL films were measured in a cell withfour parallel electrodes, where an alternating current was applied tothe outer electrodes, and the real impedance or resistance, R, wasmeasured between the two inner reference electrodes. The resistance wasdetermined from a high x-intercept of the semicircle regression of theNyquist plot. Conductivity was calculated by using the followingequation: σ=L/AR, where L and A are the distance between two innerelectrodes and the cross-sectional area of the polymer film (A=Wl; W isthe film width and l is the film thickness), respectively. Samples wereallowed to equilibrate for 2 h at each temperature at <10% RH followedby six measurements at the equilibrium condition. The values reportedare an average of these steady-state measurements. The conductivitieswere highly reproducible, and multiple measurements found an averageerror of <5%; this uncertainty is smaller than the plot symbols, soerror bars are omitted. Resulting data are shown in FIG. 17-23.

Example 3 Hydroxide Anion Exchange PIL Block and Random Copolymers

In this example, PIL block (poly(MMA-b-MEBIm-Br)) and random(poly(MMA-r-MEBIm-Br)) copolymers associated with Br⁻ at three MEBIm-Brcompositions ranging from ˜6 mole % to 17 mole % were synthesized by therevisable addition-fragmentation chain transfer (RAFT) polymerizationand the conventional free radical polymerization, respectively. Thephysical properties such as molecular weight and molecular weightdistributions of these PIL block and random copolymers are listed inTable 7. Subsequently, the PIL block and random copolymers at thehighest MEBIm-Br composition (17.3 mole %) were selected as precursorpolymers to prepare hydroxide anion exchange PIL block(poly(MMA-b-MEBIm-OH)) and random (poly(MMA-r-MEBIm-OH)) copolymers(Table 7). The anion exchange from the Br⁻ to OH⁻ form involved aheterogeneous ion exchange process where the precursor PIL polymers werecast as membranes first, then annealed and subsequently converted anionsin the already-cast and annealed membranes. Note that these precursorPIL membranes were annealed in advance prior to anion exchange.Otherwise, potential degradation reactions are likely to occur duringthe post-thermal annealing process at a high temperature (e.g., 150°C.). The elemental analysis showed that no residual Br⁻ were present inthe resulting hydroxide anion exchange PIL block and random copolymersand that the experimental values of elements were in good agreement withtheoretical calculation, indicating a successful anion exchange process.As a comparison, PIL homopolymer (poly(MEBIm-Br)) and hydroxide anionexchange PIL homopolymer (poly(MEBIm-OH)) were used as control samplesin this study.

TABLE 7 PIL Composition and Molecular Weight of PIL Block and RandomCopolymer and Homopolymer Samples Containing OH⁻ and Br⁻. PIL BlockCopolymers^(a) mol % wt % vol %^(b) M_(n) (kg mol⁻¹)^(c) M_(n) (kgmol⁻¹)^(d) PDI^(d) Poly(MMA-b-MEBIm-OH-17.3) 17.3 34.7 — 13.1 + 6.96^(e)18.25^(e) 1.26 Poly(MMA-b-MEBIm-Br-17.3) 17.3 40.0 38.2 13.1 + 8.68 18.90  1.26 Poly(MMA-b-MEBIm-Br-11.9) 11.9 30.0 28.6 13.1 + 5.60  20.38 1.41 Poly(MMA-b-MEBIm-Br-6.6) 6.6 18.4 17.4 13.1 + 2.94  18.23  1.22 PILRandom Copolymers^(a) mol % wt % vol %^(b) M_(n) (kg mol⁻¹)^(c) M_(n)(kg mol⁻¹)^(d) PDI^(d) Poly(MMA-r-MEBIm-OH-17.3) 17.3 34.7 — — 22.38^(e)2.10 Poly(MMA-r-MEBIm-Br-17.3) 17.3 40.0 38.3 — 23.17  2.10Poly(MMA-r-MEBIm-Br-12.3) 12.3 30.6 29.2 — 25.33  2.33Poly(MMA-r-MEBIm-Br-6.8) 6.6 18.8 17.8 — 23.50  2.32 PIL Homopolymer mol% wt % vol %^(b) M_(n) (kg mol⁻¹)^(c) M_(n) (kg mol⁻¹)^(d) PDI^(d)Poly(MEBIm-OH) 100 100 100 — 10.90^(e) 2.20 Poly(MEBIm-Br) 100 100 100 —13.59  2.20 ^(a)b = block copolymer, r = random copolymer, OH =hydroxide counterion, Br = bromide counterion, number denotes PILcomposition in mol % determined from ¹H NMR spectroscopy; ^(b)Volumefractions were calculated from density of PMMA (1.18 g cm⁻³) andprecursor PIL homopolymer (1.26 g cm⁻³, see Supporting Information)^(c)Calculated from ¹H NMR spectra of PMMA macro-CTA and precursor PILblock copolymers; ^(d)Determined by SEC; ^(e)Calculated from precursorPIL polymers.

Example 3.1 PIL Block and Random Copolymers (Br Counterions)

The experimental procedure to synthesize Br-containing PIL block andrandom copolymers is described above. The PIL (or MEBIm-Br) compositionand number-average molecular weight (M_(n)) of PIL block copolymers weredetermined by ¹H NMR spectroscopy using a Varian 500 MHz spectrometerwith DMSO-d₆ as the solvent. The molecular weight and polydispersityindex (PDI) of block and random PIL copolymers were measured by a sizeexclusion chromatography (SEC) system equipped with two Waters Styragelcolumns (Styragel™HR 3 and Styragel™HR 4) and a reflective index (RI)detector. A mixture of dimethylformamide (DMF) and 0.05 M lithiumbromide (LiBr) was used as a mobile phase. Polyethyleneglycol/polyethylene oxide (PEG/PEO) standards (Fluka) were used formolecular weight calibration.

Example 3.2 Solvent-Casting of PIL Block and Random Copolymers (BrCounterions)

Polymers were dissolved in anhydrous acetonitrile (10% w/w) and castonto Teflon substrates (ca. 35 mm (L)×4 mm (W)×0.525 mm (l)). Thepolymer solution was covered and the solvent was allowed to evaporateunder ambient conditions for ca. 24 h. Polymer films were subsequentlyannealed under vacuum at 150° C. for 72 h. These annealed films wereused to characterize thermal, morphological and ion conductiveproperties, and also used as precursor films to exchange into thehydroxide form via anion exchange reactions. The film thicknesses,ranging between 100 to 200 μm, were measured with a Mitutoyo digitalmicrometer with ±0.001 mm accuracy.

Example 3.3 Hydroxide Anion Exchange PIL Block and Random Copolymers

The hydroxide anion exchange PIL block copolymer(poly(MMA-b-MEBIm-OH-17.3)) was anion exchanged from its precursor PILpolymer (poly(MMA-b-MEBIm-Br-17.3)). A typical procedure of anionexchange reaction is given as follows: (1) The annealed precursorpolymer film was placed in a freshly prepared potassium hydroxide (KOH)solution (0.2 M) and purged with nitrogen for 2 h; (2) The KOH solutionwas replaced every 2 h; (3) Repeat step (2) 3 times; (4) The hydroxideexchange membrane was removed from the KOH solution and washedextensively with nitrogen-saturated DI water for 4 h, and changes offresh DI water at least four batches. The amount of residual bromideanion in the anion exchange PIL block and random copolymers wasdetermined by elemental analysis (Atlantic Microlab, Inc., Norcross,Ga.). Anal. Calcd: C, 60.46; H, 8.30; N, 3.82; Br, 0. Found: C, 56.95;H, 8.04; N, 2.83; Br, 0.00. The preparation of the anion exchange PILrandom copolymer (poly(MMA-r-MEBIm-OH-17.3)) followed the sameprocedure. Anal. Calcd: C, 60.46; H, 8.30; N, 3.82; Br, 0. Found: C,57.37; H, 7.92; N, 2.81; Br, 0.00.

Example 3.4 Characterization

Glass transition temperatures (T_(g)s) were determined by differentialscanning calorimetry (DSC; TA Instruments, Q200) over a temperaturerange of −60° C. to 180° C. at a heating/cooling rate of 10° C./minunder N₂ environment using a heat/cool/heat method. T_(g) was determinedusing the mid-point method from the second thermogram heating cycle. SeeFIG. 24.

The density of the PIL homopolymer associated with bromide anions wasestimated from the additive contribution of components to the molarvolume as reported in the literature. ^(i)The chemical structure ofpoly(MEBIm-Br) was divided into two components: poly(methylmethacrylate) (PMMA) backbone and tethered ionic part (i.e.,1-methyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide,MBIm-Br):

The additive contributions to the molar volume is:

$\frac{1}{\rho} = {\frac{w_{PMMA}}{\rho_{PMMA}} + \frac{w_{IL}}{\rho_{IL}}}$where w_(PMMA), w_(IL) denote weight fractions of PMMA and MBIm-Br ionicpart. ρ, ρ_(PMMA), ρ_(IL) are densities (g cm⁻³) of the poly(MEBIm-Br),PMMA and the MBIm-Br ionic liquid, respectively. w_(PMMA) and w_(IL),calculated from the chemical structure, are 0.312 and 0.688,respectively. The densities of PMMA and MBIm-Br IL determinedexperimentally are 1.18 g cm⁻³, and 1.30 g cm⁻³, respectively. Thus, thecalculated density for poly(MEBIm-Br) is 1.26 g cm⁻³. In this study, wealso assume that the variation of volume fraction due to the densitychange at different temperatures is negligible for these PIL block andrandom copolymers.

Example 3.5 Water Uptake

Water uptake was measured by a dynamic vapor sorption system (DVS, TAInstruments Q5000). A film sample was first dried in a vacuum oven at30° C. for 24 h and then loaded into the DVS system to precondition at0% RH and 60° C. for an additional 2 h. The film was allowed toequilibrate with humidified water vapor for 2 h to match conductivitymeasurements at the same temperature and RH. The water uptake wascalculated as follows,

$\begin{matrix}{{{Water}\mspace{14mu}{uptake}} = {\frac{W_{wet} - W_{dry}}{W_{dry}} \times 100\%}} & (1)\end{matrix}$where W_(dry) and W_(wet) are dry and wet polymer weights before andafter water uptake experiments, respectively.

TABLE 8 Morphological, Water Uptake and Conductive Properties of PILBlock and Random Copolymer and Homopolymer Samples Containing the OH⁻and Br⁻ (30° C. and 90% RH). IEC^(a) Mor- a^(b) WU^(c) σ^(d) E_(a) PILSamples mmol g⁻¹ phology nm wt % mS cm⁻¹ kJ mol⁻¹ PIL Block CopolymersPoly(MMA-b- 1.364 lamellae 16.3 13.27 20.2 MEBIm-OH-17.3) Poly(MMA-b-1.257 lamellae 18.0  1.12 28.7 MEBIm-Br-17.3) Poly(MMA-b- 0.945cylinders 11.5  0.81 30.0 MEBIm-Br-11.9) Poly(MMA-b- 0.577  8.3  0.1537.1 MEBIm-Br-6.6) PIL Random Copolymers Poly(MMA-r- 1.364 — — 18.0 1.10 25.1 MEBIm-OH-17.3) Poly(MMA-r- 1.257 — — 18.2  0.36 31.4MEBIm-Br-17.3) Poly(MMA-r- 0.970 — — 11.6  0.07 39.5 MEBIm-Br-12.3)Poly(MMA-r- 0.592 — —  8.4  0.01 41.8 MEBIm-Br-6.8) PIL HomopolymerPoly(MEBIm-OH) 3.932 — — 61.5  9.57 17.1 Poly(MEBIm-Br) 3.152 — — 34.1 0.87 24.1 ^(a)IEC = ion exchange capacity, determined from ¹H NMR;^(b)LP = lattice parameter; ^(c)WU = water uptake at 90% RH and 30° C.;^(d)σ = Ionic conductivity at 90% RH and 30° C.

Water uptake was reported as the percentage of weight gain relative toits dry polymer sample (equation 1) under equilibrium with water vaporat a certain temperature and humidity. FIG. 29 shows the water uptake ofpoly(MMA-b-MEBIm-OH-17.3), poly(MMA-r-MEBIm-OH-17.3) and poly(MEBIm-OH)(FIG. 29A) and the water uptake of their precursor PIL polymers (FIG.29B) as a function of RH at 30° C.

As shown in FIG. 29A, water uptake of all anion exchange polymer samplesincreases with increasing RH. At 30% RH, the water uptake values wererelatively low, corresponding to 2.4% for poly(MMA-b-MEBIm-OH-17.3),2.8% for poly(MMA-r-MEBIm-OH-17.3), and 8.6% for poly(MEBIm-OH),respectively. By increasing RH to 90%, the water uptake increases to16.3%, 18.0% and 61.5% accordingly (Table 8). Notice that there is anearly 6˜7 fold increase in water uptake when increasing RH from 30% to90%, indicating that RH has a significant effect on water uptake.

FIG. 29B shows a similar trend for the water uptake of precursor PILpolymers as a function of RH. With increasing RH from 30% to 90%, wateruptake values increase from 2.7% to 18.0% for poly(MMA-b-MEBIm-Br-17.3),from 2.9% to 18.2% for poly(MMA-r-MEBIm-Br-17.3), and from 5.6% to 34.1%for poly(MEBIm-Br), respectively. It is interesting to note that thereare similar water uptake values for PIL block and random copolymersassociated with either Br⁻ or OH⁻ at a same RH (e.g., 30%), but thewater uptake of the poly(MEBIm-OH) is ˜1.5 or 2 times higher than thatof poly(MEBIm-Br), indicating that the presence of MMA component reducesthe difference in water uptake of PIL copolymers for different types ofcounter anions. This is likely due to the restrained MMA component incopolymers that constrains the water uptake since the hydrophobic MMAunits do not undergo substantial segmental relaxation and still remainglassy in the presence of water.

The temperature dependence of water uptake was also investigated forboth hydroxide anion exchange PIL block and random copolymers and theirprecursor PIL polymers in this study. No significant change in wateruptake was observed in the temperature range we studied (30-60° C.) (seeFIG. 30 and FIG. 31), indicating that temperature has much less effecton water uptake compared to RH.

Both FIG. 29A and FIG. 29B also show that PIL block and randomcopolymers have similar water uptake values over the temperature andhumidity range we investigated, which was also observed at other PILcompositions (see FIG. 30), indicating that the arrangement of monomerunits in the polymer backbone has no significant effect on the wateruptake of these PIL copolymers.

Example 3.6 Ionic Conductivities

The ionic conductivities of polymer films were measured withelectrochemical impedance spectroscopy (EIS; Solartron, 1260 impedanceanalyzer, 1287 electrochemical interface, Zplot software) over afrequency range of 1 Hz to 10⁶ Hz at 200 mV. Conductivities werecollected under humidified conditions, where temperature and relativehumidity were controlled by an environmental chamber (Tenney, BTRSmodel). The in-plane conductivities of the PIL films were measured in acell with four-parallel electrodes, where an alternating current wasapplied to the outer electrodes and the real impedance or resistance, R,was measured between the two inner reference electrodes. The resistancewas determined from a high x-intercept of the semi-circle regression ofthe Nyquist plot. Conductivity was calculated by using the followingequation: σ=L/AR, where L and A are the distance between two innerelectrodes and the cross sectional area of the polymer film (A=Wl; W isthe film width and l is the film thickness), respectively. Samples wereallowed to equilibrate for 2 h at each temperature and RH followed by 6measurements at the equilibrium condition. The values reported are anaverage of these steady-state measurements.

FIG. 32 shows the ionic conductivities of poly(MMA-b-MEBIm-OH-17.3),poly(MMA-r-MEBIm-OH-17.3) and poly(MEBIm-OH) (FIG. 32A) and theirprecursor PIL polymers (FIG. 32B) as a function of temperature at 30° C.

As shown in FIG. 32A and FIG. 32B, the ionic conductivities increase 3-5orders of magnitude with increasing RH from 30% to 90%, indicating thatthe ionic conductivity of these hydrophilic PIL samples is stronglydependent on RH. This can be explained by a significant increase inwater uptake (FIG. 29) and a corresponding enhanced hydration level, iondissociation and hydrophilic PIL conducting channels to facilitate iontransport at a high RH. For example, the PIL domain size inpoly(MMA-b-MEBIm-Br) enlarges from 11.5 to 16.7 nm (45% increase) withincreasing RH from 30% to 90% (FIG. 4).

FIG. 32 also shows that the block copolymer containing either MEBIm-OH(FIG. 32A) or MEBIm-Br (FIG. 32B) has much higher ionic conductivitythan its random counterpart despite the same PIL composition and wateruptake. This is especially evident at a relatively low RH where at 30%RH the conductivity of the block copolymer is about two orders ofmagnitude higher than that of the random copolymer. With increasing RH,the difference becomes less pronounced. This trend is also seen at otherlower PIL compositions (see FIG. 34).

To better understand the difference in ionic conductivity between blockand random copolymers, it is important to compare the morphologydifference. Note that in PIL block copolymers, the hydrophilic ILs(either MEBIm-OH or MEBIm-Br) are covalently tethered next to each otherand conducting ions (either OH⁻ or Br⁻) are not only locallyconcentrated, but also self-assembled to form a periodic nanostructuredlamellar morphology with connected ion-conducting domains due to thestrong microphase separation of hydrophilic and hydrophobic blocks. Incontrast, ionic sites are far separated by non-ionic MMA units in thePIL random counterparts. Specifically, on average, there are ca. 5 MMAunits located between two ionic sites along the polymer backbone at thePIL composition of 17.3 mole %. Moreover, PIL random copolymers onlyexhibit a homogeneous morphology without microphase separatednanostructures and do not form distinct ion conducting domains. Theseresult in a higher activation energy required for ion transport and asignificant decrease in ionic conductivity compared to PIL blockcopolymers (Table 8). Therefore, the difference in ion transport betweenthe PIL block and random copolymers is mainly driven by themorphological difference between the two.

Interestingly, FIG. 32 also shows that the ionic conductivities of thePIL block copolymers are greater than their homopolymers at 90% RH and30° C. The difference in ionic conductivity is further clearlyillustrated in FIG. 33 where the ionic conductivities are plotted as afunction of temperature at 90% RH. FIG. 33 shows that the ionicconductivities of the block copolymers are higher than theirhomopolymers over a wide temperature range. At 80° C., the ionicconductivities of poly(MMA-b-MEBIm-OH-17.3) (25.46 mS cm⁻¹) andpoly(MMA-b-MEBIm-Br-17.3)) (5.67 mS cm⁻¹) are ca. 66% and 60% higherthan their homopolymers, respectively. This indicates that factors otherthan ion content influence ion transport. Although the detailedmechanism of enhanced ion conduction was not fully understood, thenanostructured hydrophilic ion-conducting channels and reducedtortuosity of ion-conducting paths compared to homopolymers could be areason.

FIG. 33 also shows that different from hydrophobic PILs where iontransport is significantly coupled with polymer segmental relaxation andexhibits the Vogel-Fulcher-Tammann (VFT) behavior, water-assisted iontransport of PIL block and random copolymers exhibited the Arrheniusbehavior as a typical proton exchange membrane. The activation energiesfor the transport of OH⁻ in PIL block and random copolymers andhomopolymer are 20.2, 25.1 and 17.1 kJ mol⁻¹, respectively. As acomparison, the activation energies for the transport of Br⁻ in PILblock and random copolymers and homopolymer are 28.7, 31.4, and 24.1 kJmol⁻¹, respectively. A bigger anion size of Br⁻ accounts for the higheractivation energy for the transport of Br⁻ as compared to OH⁻. Noticethat with decreasing PIL composition, the activation energy increasesfor precursor PIL block and random copolymers (Table 8), indicating alager barrier of ion transport at a lower composition due to a low wateruptake and reduced connectivity of ionic domains.

Example 3.7 General Remarks

This study revealed the influence of nanostructured morphology onwater-assistant ion transport in hydroxide anion exchange polymerizedionic liquid (PIL) block copolymers (anion exchange membranes, AEMs) andtheir precursor PIL block copolymers by comparing to the randomcounterparts and homopolymers. The block copolymer AEMs consisted of animidazolium-based ion-conducting component(1-[(2-methacryloyloxy)ethyl]-3-butylimidazolium hydroxide (MEBIm-OH))and a non-ionic structural-supporting component (methyl methacrylate,MMA). The microphase-separated morphologies of these PIL blockcopolymers were monitored by small angle X-ray scattering under both dryand humidified conditions. These well-ordered periodic nanostructureswere also confirmed by transmission electron microscopy. Combing furtherstudies on water uptake and ionic conductivity, it was concluded thatwell-connected and confined hydrophilic PIL nanostructured conductingchannels were the major factor that facilitates ion conduction andprovided superior ionic conductivity of the PIL block copolymerscompared to the random counterparts and homopolymers. These anionexchange PIL block copolymers are attractive for further exploration asa new type of AEMs in the use of alkaline fuel cells.

The solid-state alkaline fuel cell (AFC), utilizing a solid-state anionexchange membrane (AEM) rather than a liquid electrolyte to transporthydroxide anions (OH⁻), has recently attracted increased attention dueto inherent advantages over proton exchange membrane (PEM) fuel cells.The benefits include cost reduction (e.g., cheaper nickel or silvercatalysts to replace expensive platinum catalysts), wider choices offuels (e.g., methanol), and simplified water management. In addition,the utilization of AEMs in AFCs can resolve known issues encounteredwith liquid electrolytes such as device corrosion, electrolyte leakageand carbonate precipitation. However, one critical and challenging issuethat limits the wide scale use of current AEMs for solid-state AFCs isthe chemical stability of AEMs, especially at dehydrated conditions andelevated temperatures.

It is certain that ionic conductivity of AEMs is one of the key factorsthat determine the device performance of AFCs. Particularly,understanding in situ morphologies under humidified conditions is moreimportant since water plays a crucial role in water-assistant iontransport.

The purpose of this work was to study the morphologies ofimidazolium-based PIL block copolymers including hydroxide anionexchange PIL block copolymers (block copolymer AEMs) and their precursorPIL block copolymers, and the impact of morphology on ion transport. Themodel PIL block copolymers were composed of an IL component (either1-[(2-methacryloyloxy)ethyl]-3-butylimidazolium hydroxide (MEBIm-OH) or1-[(2-methacryloyloxy)ethyl]-3-butylimidazolium bromide (MEBIm-Br)) anda non-ionic component (methyl methacrylate, MMA). In these PIL diblockcopolymers, the PIL block was very hydrophilic, conducting either OH⁻ orbromide anions (Br⁻) under humidified conditions, while the PMMA blockwas hydrophobic, providing mechanical support for the membrane. Tobetter understand the impact of nanostructured morphology on ionicconductivity, PIL random copolymers containing either OH⁻ or Br⁻ atsimilar PIL compositions were prepared and their PIL homopolymers wereused for comparison. In this study, the in situ morphology of PIL blockand random block copolymers was measured by X-ray scatting in anenvironmental chamber (EC), which allows us to monitor the change ofdomain sizes at a certain elevated temperature and relative humidity(RH). As expected, despite a similar PIL composition, the ionicconductivities of PIL block copolymers (either OH⁻ or Br⁻) weresignificantly higher than their random counterparts although both hadsimilar water uptake values at a same humidified condition. Moreinterestingly, they have higher ionic conductivities than homopolymers.This superior ionic conductivity was mainly attributedmicrophase-separated morphology with well-ordered nanostructures andgood connectivity of nanostructured conductive domains.

It is to be understood that while the invention has been described inconjunction with the preferred specific embodiments thereof, that theforegoing description and the examples that follow are intended toillustrate and not limit the scope of the invention. It will beunderstood by those skilled in the art that various changes may be madeand equivalents may be substituted without departing from the scope ofthe invention, and further that other aspects, advantages andmodifications will be apparent to those skilled in the art to which theinvention pertains. In addition to the embodiments described herein, thepresent invention contemplates and claims those inventions resultingfrom the combination of features of the invention cited herein and thoseof the cited prior art references which complement the features of thepresent invention. Similarly, it will be appreciated that any describedmaterial, feature, or article may be used in combination with any othermaterial, feature, or article, and such combinations are consideredwithin the scope of this invention.

The disclosures of each patent, patent application, and publicationcited or described in this document are hereby incorporated herein byreference, each in its entirety, for all purposes.

What is claimed:
 1. A block copolymer comprising a first and secondblock, said first block comprising an acrylate or methacrylatederivative; said second block comprising (a) polymerized ionic liquid,said polymerized ionic liquid comprising a tethered ionic liquid cationand a mobile anion, and (b) a lithium ion salt of said mobile anion,wherein said block copolymer exhibits at least one region of nanophaseseparation having at least one region of a periodic nanostructuredlamellar morphology with connected ion-conducting domains.
 2. The blockcopolymer of 1, wherein the connected ion-conducting domains extend inthree-dimensions throughout the block copolymer.
 3. The block copolymerof claim 1, wherein the periodicity of the nanostructured lamellarmorphology is characterized by ordered domains having lattice parameterdimensions in the range of about 5 to about 50 nm, as measured by smallangle X-ray scattering.
 4. The block copolymer of claim 1, wherein theperiodic nanostructured lamellar morphology with connectedion-conducting domains allows for the conduction of lithium ions throughthe block copolymer.
 5. The block copolymer of claim 1, wherein thefirst block comprises a repeating unit:

where R^(1A), R^(2A), R^(3A), and R^(4A) are independently H or C₁₋₁₂alkyl.
 6. The block copolymer of claim 5, wherein R^(1A) and R^(2A) areboth H.
 7. The block copolymer of claim 5, wherein both R^(3A) andR^(4A) are both C₁₋₆ alkyl.
 8. The block copolymer of claim 5, whereinR^(1A) and R^(2A) are both H and R^(3A) and R^(4A) are both methyl. 9.The block copolymer of claim 1, wherein the first block has a numberaverage molecular weight in the range of about 1000 to about 50000Daltons.
 10. The block copolymer of claim 1, wherein the tethered ionicliquid cation comprises an optionally alkyl-substituted imidazolium,pyridinium, pyrrolidinum cation, or combination thereof.
 11. The blockcopolymer of claim 1, wherein the polymerized ionic liquid comprises aC₃₋₆ alkyl-substituted imidazolium cation.
 12. The block copolymer ofclaim 1, wherein the cation of the polymerized is tethered by acarboalkoxy linking group.
 13. The block copolymer of claim 1, whereinthe second block comprising a polymerized ionic liquid comprises arepeating unit:

where R^(5A), R^(6A), R^(7A), and R^(8A) are independently H or C₁₋₆alkyl; and n is in a range of 0 to
 20. 14. The block copolymer of claim13, wherein R^(5A) and R^(6A) are both H.
 15. The block copolymer ofclaim 13, wherein R^(7A) and R^(8A) are both C₁₋₄ alkyl.
 16. The blockcopolymer of claim 13, wherein R^(5A) and R^(6A) are both H, R^(7A) ismethyl, and R^(8A) is n-butyl, and n=1.
 17. The block copolymer of claim1, wherein the block copolymer is substantially anhydrous.
 18. The blockcopolymer of claim 1, wherein the second block further comprises asolvent comprising ethylene carbonate, ethylene glycol, polyethyleneglycol, propylene glycol, propylene carbonate, butylene carbonate,dimethyl carbonate, diethyl carbonate, methylethyl carbonate, dipropylcarbonate, γ-butyrolactone, dimethoxyethane, diethoxyethane, or amixture thereof.
 19. The block copolymer of claim 1, wherein the mobileanion is an alkyl phosphate, biscarbonate, bistriflimide, N(SO₂C₂F₅)₂ ⁻,N(SO₂CF₃)(SO₂C₄F₉)⁻, carbonate, chlorate, formate, glycolate,perchlorate, hexasubstituted phosphate, tetra-substituted borate,tosylate, or triflate or combination thereof.
 20. The block copolymer ofclaim 1, further comprising a mobile ionic liquid comprising at leastone optionally substituted imidazolium, pyridinium, pyrrolidinum cationand at least one alkyl phosphate, biscarbonate, bistriflimide,N(SO₂C₂F₅)₂ ⁻, N(SO₂CF₃)(SO₂C₄F₉)⁻, carbonate, chlorate, formate,glycolate, perchlorate, hexasubstituted phosphate; tetra-substitutedborate), tosylate, or triflate anion.
 21. The block copolymer of claim1, wherein the polymerized ionic liquid block has a number averagemolecular weight in the range of about 1000 to about 50000 Daltons. 22.The block copolymer of claim 1, wherein the block copolymer has a numberaverage molecular weight in a range of about 5000 to about 25,000Daltons, as measured by size exclusion chromatography.
 23. The blockcopolymer of claim 1, wherein the block copolymer has a number averagemolecular weight which is characterized as exhibiting a polydispersityin the range of about 1 to about 1.5, as measured by size exclusionchromatography.
 24. The block copolymer of claim 1, wherein thepolymerized ionic liquid block is present in a range of about 5 mole %to about 95 mole % of the total block copolymer.
 25. A lithium ionbattery membrane comprising a block copolymer of claim
 1. 26. A membraneelectrode assembly comprising a membrane of claim
 25. 27. A lithium ionbattery comprising a membrane of claim
 25. 28. The block copolymer ofclaim 13, wherein n is about 10.